2,4,6-Phenyl-substituted cyclic ketoenols

ABSTRACT

The present invention relates to novel 2,4,6-phenyl-substituted cyclic ketoenols of the formula (I) 
     
       
         
         
             
             
         
       
         
         
           
             in which W, X, Y and CKE have the meanings given in the disclosure, to a plurality of processes for their preparation and to their use as pesticides and/or herbicides. 
           
         
       
    
     The invention further relates to selectively herbicidal compositions containing 2,4,6-phenyl-substituted cyclic ketoenols and a compound which improves crop plant tolerance.

The present invention relates to new 2,4,6-phenyl-substituted cyclicketoenols, to a plurality of processes for their preparation, and totheir use as pesticides and/or herbicides. The invention furthermorerelates to selectively herbicidal compositions comprising firstly2,4,6-phenyl-substituted cyclic ketoenols and secondly a compound whichimproves crop plant tolerance.

Pharmaceutical properties have been previously described or3-acyl-pyrrolidine-2,4-diones (S. Suzuki et al. Chem. Pharm. Bull. 151120 (1967)). Furthermore, N-phenylpyrrolidine-2,4-diones have beensynthesized by R. Schmierer and H. Mildenberger (Liebigs Ann. Chem.1985, 1095). A biological activity of these compounds has not beendescribed.

EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of a similarstructure (3-aryl-pyrrolidine-2,4-diones), of which. however, noherbicidal, insecticidal or acaricidal action has been disclosed.Unsubstituted, bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives(EP-A-355 599, EP-415 211 and JP-A-12-053 670) and substitutedmonocyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A-377 893 andEP-A-442 077) having a herbicidal, insecticidal or acaricidal actionhave been disclosed.

There have also been disclosed polycyclic 3-arylpyrrolidine-2,4-dionederivatives (EP-A-442 073) and 1H-arylpyrrolidine-dione derivatives(EP-A-456 063, EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885,WO 94/01 997, WO 95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395,WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 97/43275, WO98/05638, WO 98/06721, WO 98/25928, WO 99/16748, WO 99/24437, WO99/43649, WO 99/48869 and WO 99/55673, WO 01/17972, WO 01/23354, WO01/74770.

It has been disclosed that certain substituted Δ³-dihydrofuran-2-onederivatives have herbicidal properties (cf. DE-A-4 014 420). Thesynthesis of the tetronic acid derivatives used as starting compounds(such as, for example,3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)-Δ³-dihydrofuran-2-one)is also described in DE-A-4 014 420. Compounds of a similar structurewithout any mention of an insecticidal and/or acaricidal activity areknown from the publication Campbell et al., J. Chem. Soc., Perkin Trans.1, 1985, (8) 1567-76. 3-Aryl-Δ³-dihydrofuranone derivatives havingherbicidal, acaricidal and insecticidal properties are furthermoredisclosed in EP-A-528 156, EP-A-0 647 637, WO 95/26 345, WO 96/20 196,WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO98/05638, WO 98/25928, WO 99/16748, WO 99/43649, WO 99/48869, WO99/55673, WO 01/17972, WO 01/23354 and WO 01/74770.3-Aryl-Δ³-dihydrothiophenone derivatives are also known (WO 95/26 345,96/25 395, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 98/05638, WO98/25928, WO 99/16748, WO 99/43649, WO 99/48869, WO 99/55673, WO01/17972, WO 01/23354 and WO 01/74770).

Certain phenyl-pyrone derivatives which are unsubstituted in the phenylring have already been disclosed (cf. A. M. Chirazi, T. Kappe and E.Ziegler, Arch. Pharm. 309, 558 (1976) and K.-H. Boltze and K.Heidenbluth, Chem. Ber. 91 2849), a possible use of these compounds aspesticides not being mentioned. Phenyl-pyrone derivatives which aresubstituted in the phenyl ring and have herbicidal, acaricidal andinsecticidal properties are described in EP-A-588 137, WO 96/25 395, WO96/35 664, WO 97/01 535, WO 97/02 243, WO 97/16 436, WO 97/19 941, WO97/36 868, WO 98/05638, WO 99/43649, WO 99/48869, WO 99/55673, WO01/17972 and WO 01/74770.

Certain 5-phenyl-1,3-thiazine derivatives which are unsubstituted in thephenyl ring have already been disclosed (cf. E. Ziegler and E. Steiner,Monatsh. 25, 147 (1964), R. Ketcham. T. Kappe and E. Ziegler, J.Heterocycl. Chem. 10, 223 (1973)), a possible use of these compounds aspesticides not being mentioned. 5-Phenyl-1,3-thiazine derivatives whichare substituted in the phenyl ring and have a herbicidal, acaricidal andinsecticidal action are described in WO 94/14 785, WO 96/02 539, WO96/35 664, WO 97/01 535, WO 97/02 243, WO 97/02 243, WO 97/36 868, WO99/05638, WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972 and WO01/74770.

It is known that certain substituted 2-arylcyclopentanediones haveherbicidal, insecticidal and acaricidal properties (cf., for example,U.S. Pat. Nos. 4,283,348; 4,338,122; 4,436,666; 4,526,723; 4,551,547;4,632,698, WO 96/01 798; WO 96/03 366, WO 97/14 667 and also WO98/39281, WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972 and WO01/747770). Moreover, compounds with similar substitutions are known;3-hydroxy-5,5-dimethyl-2-phenylcyclopent-2-en-1-one from the publicationMicklefield et al., Tetrahedron, (1992), 7519-26 and the natural productinvolutin(−)-cis-5-(3,4-dihydroxyphenyl)-3,4-dihydroxy-2-(4-hydroxyphenyl)-cyclopent-2-en-onefrom the publication Edwards et al., J. Chem. Soc. S, (1967), 405-9. Aninsecticidal or acaricidal activity is not described. Moreover,2-(2,4,6-trimethylphenyl)-1,3-indanedione is known from the publicationJ. Economic Entomology, (1973), 584 and the Offenlegungsschrift DE-A-2361 084, with herbicidal and acaricidal activities being detailed.

It is known that certain substituted 2-arylcyclohexanediones haveherbicidal, insecticidal and acaricidal properties (U.S. Pat. Nos.4,175,135, 4,209,432, 4,256,657, 4,256,658, 4,256,659, 4,257,858,4,283,348, 4,303,669, 4,351,666, 4,409,153, 4,436,666, 4,526,723,4,613,617, 4,659,372, DE-A 2 813 341, and also Wheeler, T. N., J. Org.Chem. 44, 4906 (1979)), WO 99/43649, WO 99/48869, WO 99/55673, WO01/17972 and WO 01/74770).

It is known that certain substituted 4-aryl-pyrazolidine-3,5-diones haveacaricidal, insecticidal and herbicidal properties (cf., for example, WO92/16 510, EP-A-508 126, WO 96/11 574, WO 96/21 652, WO 99/47525, WO01/17 351, WO 01/17 352, WO 01/17 353, WO 01/17 972, WO 01/17 973, WO03/028 466 and WO 03/062 244).

However, the activity and range of action of these compounds is notalways entirely satisfactory, in particular when low rates andconcentrations are applied. Furthermore, these compounds are not alwayssufficiently well tolerated by plants.

There have now been found new compounds of the formula (I)

in which

-   W represents alkoxy, halogenoalkoxy, alkoxyalkyloxy,    alkoxy-bis-alkyloxy or optionally substituted    cycloalkylalkanediyloxy, which can optionally be interrupted by    hetero atoms,-   X represents alkyl,-   Y represents chlorine, bromine or iodine,-   CKE represents one of the groups

in which

-   A represents hydrogen, or represents alkyl, alkenyl, alkoxyalkyl or    alkylthioalkyl, each of which is optionally substituted by halogen,    or represents saturated or unsaturated, optionally substituted    cycloalkyl in which at least one ring atom is optionally replaced by    a hetero atom, or represents aryl, arylalkyl or hetaryl, each of    which is optionally substituted by halogen, alkyl, halogenoalkyl,    alkoxy, halogenoalkoxy, cyano or nitro,-   B represents hydrogen, alkyl or alkoxyalkyl, or-   A and B together with the carbon atom to which they are bonded    represent a saturated or unsaturated, unsubstituted or substituted    cycle which optionally contains at least one hetero atom,-   D represents hydrogen or an optionally substituted radical from the    series consisting of alkyl, alkenyl, alkinyl, alkoxyalkyl, saturated    or unsaturated cycloalkyl in which optionally one or more ring    members are replaced by hetero atoms; arylalkyl, aryl, hetarylalkyl    or hetaryl, or-   A and D together with the atoms to which they are bonded represent a    saturated or unsaturated cycle which is unsubstituted or substituted    in the A, D moiety and which optionally contains at least one (in    the case of CKE=8, a further) hetero atom, or-   A and Q¹ together represent alkanediyl or alkenediyl which are    optionally substituted by hydroxyl or by in each case optionally    substituted alkyl, alkoxy, alkylthio, cycloalkyl, benzyloxy or aryl,    or-   Q¹ represents hydrogen or alkyl,-   Q², Q⁴, Q⁵ and Q⁶ independently of one another represent hydrogen or    alkyl,-   Q³ represents hydrogen, optionally substituted alkyl, alkoxyalkyl,    alkylthioalkyl, optionally substituted cycloalkyl (in which a    methylene group is optionally replaced by oxygen or sulphur) or    optionally substituted phenyl, or-   Q³ and Q⁴ together with the carbon atom to which they are bonded    represent a saturated or unsaturated, unsubstituted or substituted    cycle which optionally contains a hetero atom,-   G represents hydrogen (a) or one of the groups

-   -   where    -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur,    -   M represents oxygen or sulphur,    -   R¹ represents alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or        polyalkoxyalkyl, each of which is optionally substituted by        halogen, or represents cycloalkyl which can be interrupted by at        least one hetero atom and which is optionally substituted by        halogen, alkyl or alkoxy, or represents in each case optionally        substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or        hetaryloxyalkyl,    -   R² represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl,        each of which is optionally substituted by halogen, or        represents in each case optionally substituted cycloalkyl,        phenyl or benzyl,    -   R³, R⁴ and R⁵ independently of one another represent alkyl,        alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or        cycloalkylthio, each of which is optionally substituted by        halogen, or represent in each case optionally substituted        phenyl, benzyl, phenoxy or phenylthio,    -   R⁶ and R⁷ independently of one another represent hydrogen, or        represent alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl,        each of which is optionally substituted by halogen, or represent        optionally substituted phenyl, or represent optionally        substituted benzyl, or together with the N atom to which they        are bonded represent a cycle which is optionally interrupted by        oxygen or sulphur.

Depending on the nature of the substituents also, the compounds of theformula (I) can be present in the form of geometric and/or opticalisomers or variously composed isomer mixtures, which can optionally beseparated in the customary manner. The present invention relates to thepure isomers and also to the isomer mixtures, to their preparation,their use, and to compositions comprising them. However, the followingtext will always mention compounds of the formula (I), for the sake ofsimplicity, even though this is to be understood as meaning the purecompounds and, if appropriate, also mixtures containing variousproportions of isomeric compounds.

Taking into consideration the meanings (1) to (8) of the CKE group, thefollowing main structures (I-1) to (I-8) result:

in which

-   A, B, D, G, Q¹, Q², Q³, Q⁴, Q⁵, W, X and Y have the abovementioned    meanings.

Taking into consideration the various meanings (a), (b), (c), (d), (e),(f) and (g) of group G, the following main structures (I-1-a) to (I-1-g)result if CKE represents group (1)

in which

-   A, B, D, E, L, M, W, X, Y, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the    abovementioned meanings.

Taking into consideration the various meanings (a), (b), (c), (d), (e),(f) and (g) of group G, the following main structures (I-2-a) to (I-2-g)result if CKE represents group (2)

in which

-   A, B, E, L, M, W, X, Y, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the    above-mentioned meanings.

Taking into consideration the various meanings (a), (b), (c), (d), (e),(f) and (g) of group G, the following main structures (I-3-a) to (I-3-g)result if CKE represents group (3)

in which

-   A, B, E, L, M, W, X, Y, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the    abovementioned meanings.

Depending on the position of the substituent G, the compounds of theformula (I-4) can exist in the two isomeric forms of the formulae(I-4-A) and (I-4-B)

which is intended to be expressed by the broken line in formula (I-4).

The compounds of the formulae (I-4-A) and (I-4-B) can exist as mixturesand also in the form of their pure isomers. If appropriate, mixtures ofthe compounds of the formulae (I-4-A) and (I-4-B) can be separated in amanner known per se using physical methods, for example bychromatographic methods.

For reasons of improved clarity, the following text will always mentiononly one of the isomers which are possible. This does not exclude thefact that the compounds can be present, if appropriate, in the form ofthe isomer mixtures or in the respective other isomeric form.

Taking into consideration the various meanings (a), (b), (c), (d), (e),(f) and (g) of group G, the following main structures (I-4-a) to (I-4-g)result if CKE represents group (4)

in which

-   A, D, E, L, M, W, X, Y, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the    above-mentioned meanings.

Taking into consideration the various meanings (a), (b), (c), (d), (e),(f) and (g) of group G, the following main structures (I-5-a) to (I-5-g)result if CKE represents group (5)

in which

-   A, E, L, M, W, X, Y, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the    abovementioned meanings.

Depending on the position of the substituent G, the compounds of theformula (I-6) can exist in the two isomeric forms of the formulae(I-6-A) and (I-6-B)

which is intended to be expressed by the broken line in formula (I).

The compounds of the formulae (I-6-A) and (I-6-B) can exist as mixturesand also in the form of their pure isomers. If appropriate, mixtures ofthe compounds of the formulae (I-6-A) and (I-6-B) can be separated usingphysical methods, for example by chromatographic methods.

For reasons of improved clarity, the following text will always mentiononly one of the isomers which are possible. This does not exclude thefact that the compounds can be present, if appropriate, in the form ofthe isomer mixtures or in the respective other isomeric form.

Taking into consideration the various meanings (a), (b), (c), (d), (e),(f) and (g) of group G, the following main structures (I-6-a) to (I-6-g)result:

in which

-   A, B, Q¹, Q², E, L, M, W, X, Y, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have    the abovementioned meanings.

Depending on the position of the substituent G, the compounds of theformula (I-7) can exist in the two isomeric forms of the formulae(I-7-A) and (I-7-B), which is intended to be expressed by the brokenline in formula (I-7):

The compounds of the formulae (I-7-A) and (I-7-B) can exist as mixturesand also in the form of their pure isomers. If appropriate, mixtures ofthe compounds of the formulae (I-7-A) and (I-7-B) can be separated usingphysical methods, for example by chromatographic methods.

For reasons of improved clarity, the following text will always mentiononly one of the isomers which are possible. This includes the fact thatthe compound in question can be present, if appropriate, in the form ofan isomer mixture or in the respective other isomeric form.

Taking into consideration the various meanings (a), (b), (c), (d), (e),(f) and (g) of group G, the following main structures (I-7-a) to (I-7-g)result:

in which

-   A, B, E, L, M, Q³, Q⁴, Q⁵, Q⁶, W, X, Y, R¹, R², R³, R⁴, R⁵, R⁶ and    R⁷ have the abovementioned meanings.

Depending on the position of the substituent G, the compounds of theformula (I-8) can exist in the two isomeric formulae (I-8-A) and(I-8-B),

which is intended to be expressed by the broken line in formula (I-8).

The compounds of the formulae (I-8-A) and (I-8-B) can exist as mixturesand also in the form of the pure isomers. If appropriate, mixtures ofthe compounds of the formula (I-8-A) and (I-8-B) can be separated in amanner known per se using physical methods, for example bychromatographic methods.

For reasons of improved clarity, the following text will always mentiononly one of the isomers which are possible. This does not exclude thefact that the compounds can be present, if appropriate, in the form ofthe isomer mixtures or in the respective other isomeric form.

Taking into consideration the various meanings (a), (b), (c), (d), (e),(f) and (g) of group G, the following main structures (I-8-a) to (I-8-g)result if CKE represents group (8)

in which

-   A, D, E, L, M, W, X, Y, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the    abovementioned meanings.

Furthermore, it has been found that the new compounds of the formula (I)are obtained by one of the processes described below:

-   (A) Substituted 3-phenylpyrrolidine-2,4-diones or their enols of the    formula (I-1-a)

-   -   in which    -   A, B, D, W, X and Y have the abovementioned meanings are        obtained when    -   N-acylamino acid esters of the formula (II)

-   -   in which    -   A, B, D, W, X and Y have the abovementioned meanings    -   R⁸ represents alkyl (preferably C₁-C₆-alkyl)    -   are subjected to an intramolecular condensation reaction in the        presence of a diluent and in the presence of a base.

-   (B) Furthermore, it has been found that substituted    3-phenyl-4-hydroxy-Δ³-dihydrofuranone derivatives of the formula    (I-2-a)

-   -   in which    -   A, B, W, X and Y have the abovementioned meanings    -   are obtained when    -   carboxylic esters of the formula (III)

-   -   in which    -   A, B, W, X, Y and R⁸ have the abovementioned meanings    -   are subjected to an intramolecular condensation reaction in the        presence of a diluent and in the presence of a base.

-   (C) Furthermore, it has been found that substituted    3-phenyl-4-hydroxy-Δ³-dihydrothiophenone derivatives of the formula    (I-3-a)

-   -   in which    -   A, B, W, X and Y have the abovementioned meanings    -   are obtained when    -   β-ketocarboxylic esters of the formula (IV)

-   -   in which    -   A, B, W, X, Y and R⁸ have the abovementioned meanings and    -   V represents hydrogen, halogen, alkyl (preferably C₁-C₆-alkyl)        or alkoxy (preferably C₁-C₈-alkoxy)    -   are subjected to intramolecular cyclization, if appropriate in        the presence of a diluent and in the presence of an acid.

-   (D) Furthermore, it has been found that the new substituted    3-phenyl-pyrone derivatives of the formula (I-4-a)

-   -   in which    -   A, D, W, X and Y have the abovementioned meanings    -   are obtained when    -   carbonyl compounds of the formula (V)

-   -   in which    -   A and D have the abovementioned meanings    -   or their silyl enol ethers of the formula (Va)

-   -   in which    -   A, D and R⁸ have the abovementioned meanings    -   are reacted with ketene acid halides of the formula (VI)

-   -   in which    -   W, X and Y have the abovementioned meanings and    -   Hal represents halogen (preferably chlorine or bromine),    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid acceptor.

Furthermore, it has been found

-   (E) that the new substituted phenyl-1,3-thiazine derivatives of the    formula (I-5-a)

-   -   in which    -   A, W, X and Y have the abovementioned meanings    -   are obtained when thioamides of the formula (VII)

-   -   in which    -   A has the abovementioned meaning    -   are reacted with ketene acid halides of the formula (VI)

-   -   in which    -   Hal, W, X and Y have the abovementioned meanings,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid acceptor.

Furthermore, it has been found

-   (F) that compounds of the formula (I-6-a)

-   -   in which    -   A, B, Q¹, Q², W, X and Y have the abovementioned meanings    -   are obtained when    -   ketocarboxylic esters of the formula (VIII)

-   -   in which    -   A, B, Q¹, Q², W, X and Y have the abovementioned meanings and    -   R⁸ represents alkyl (in particular C₁-C₈-alkyl)    -   are subjected to an intramolecular cyclization reaction, if        appropriate in the presence of a diluent and in the presence of        a base.

Furthermore, it has been found

-   (G) that compounds of the formula (I-7-a)

-   -   in which    -   A, B, Q³, Q⁴, Q⁵, Q⁶, W, X and Y have the abovementioned        meanings    -   are obtained when    -   6-aryl-5-ketohexanoic esters of the formula (IX)

-   -   in which    -   A, B, Q³, Q⁴, Q⁵, Q⁶, W, X and Y have the abovementioned        meanings    -   and    -   R⁸ represents alkyl (preferably C₁-C₆-alkyl)    -   are subjected to an intramolecular condensation reaction in the        presence of a diluent and in the presence of a base.

-   (H) Furthermore, it has been found that the compounds of the formula    (I-8-a)

-   -   in which    -   A, D, W, X and Y have the abovementioned meanings    -   are obtained when    -   compounds of the formula (X)

-   -   in which    -   A and D have the abovementioned meanings    -   α) are reacted with compounds of the formula (VI)

-   -   in which    -   Hal, X, Y and W have the abovementioned meanings,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid acceptor, or    -   β) are reacted with compounds of the formula (XI)

-   -   in which    -   W, X and Y have the abovementioned meanings,    -   and U represents NH₂ or O—R⁸, where R⁸ has the abovementioned        meaning,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of a base, or    -   γ) are reacted with compounds of the formula (XII)

-   -   in which    -   A, D, W, X, Y and R⁸ have the abovementioned meanings,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of a base.

Furthermore, it has been found

-   (I) that the compounds of the formulae (I-1-b) to (I-8-b) shown    above in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R¹, W, X, and Y have    the above-mentioned meanings are obtained when compounds of the    formulae (I-1-a) to (I-8-a) shown above in which A, B, D, Q¹, Q²,    Q³, Q⁴, Q⁵, Q⁶, W, X and Y have the abovementioned meanings    are reacted in each case    -   (α) with acid halides of the formula (XIII)

-   -   in which    -   R¹ has the abovementioned meaning and    -   Hal represents halogen (in particular chlorine or bromine),    -   or    -   (β) with carboxylic anhydrides of the formula (XIV)

R¹—CO—O—CO—R¹  (XIV)

-   -   in which    -   R¹ has the abovementioned meaning,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid-binding agent;

-   (J) that the compounds of the formulae (I-1-c) to (I-8-c) shown    above in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R², M, W, X and Y    have the abovementioned meanings and L represents oxygen are    obtained when compounds of the formulae (I-1-a) to (I-8-a) shown    above in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X and Y have the    abovementioned meanings are reacted in each case    -   with chloroformic esters or chloroformic thioesters of the        formula (XV)

R²-M-CO—Cl  (XV)

-   -   in which    -   R² and M have the abovementioned meanings,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid-binding agent;

-   (K) that compounds of the formulae (I-1-c) to (I-8-c) shown above in    which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R², M, W, X and Y have the    abovementioned meanings and L represents sulphur are obtained when    compounds of the formulae (I-1-a) to (I-8-a) shown above in which A,    B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X and Y have the abovementioned    meanings are reacted in each case    -   with chloromonothioformic esters or chlorodithioformic esters of        the formula (XVI)

-   -   in which    -   M and R² have the abovementioned meanings,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid-binding agent,    -   and

-   (L) that compounds of the formulae (I-1-d) to (I-8-d) shown above in    which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R³, W, X and Y have the    abovementioned meanings are obtained when compounds of the formulae    (I-1-a) to (I-8-a) shown above in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵,    W, X and Y have the abovementioned meanings are reacted in each case    -   with sulphonyl chlorides of the formula (XVII)

R³—SO₂—Cl  (XVII)

-   -   in which    -   R³ has the abovementioned meaning,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid-binding agent,

-   (M) that compounds of the formulae (I-1-e) to (I-8-e) shown above in    which A, B, D, L, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R⁴, R⁵, W, X and Y have    the abovementioned meanings are obtained when compounds of the    formulae (I-1-a) to (I-8-a) shown above in which A, B, D, Q¹, Q²,    Q³, Q⁴, Q⁵, Q⁶, W, X and Y have the abovementioned meanings are    reacted in each case    -   with phosphorus compounds of the formula (XVIII)

-   -   in which    -   L, R⁴ and R⁵ have the abovementioned meanings and    -   Hal represents halogen (in particular chlorine or bromine),    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid-binding agent,

-   (N) that compounds of the formulae (I-1-f) to (I-8-0 shown above in    which A, B, D, E, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X and Y have the    abovementioned meanings are obtained when compounds of the formulae    (I-1-a) to (I-8-a) in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X    and Y have the abovementioned meanings are in each case reacted    -   with metal compounds or amines of the formulae (XIX) or (XX)

Me(OR¹⁰)_(t)  (XIX)

-   -   in which    -   Me represents a mono- or divalent metal (preferably an alkali        metal or alkaline earth metal, such as lithium, sodium,        potassium, magnesium or calcium), or represents an ammonium ion

-   -   t represents the number 1 or 2 and    -   R¹⁰, R¹¹ and R¹² independently of one another represent hydrogen        or alkyl (preferably C₁-C₈-alkyl),    -   if appropriate in the presence of a diluent,

-   (O) that compounds of the formulae (I-1-g) to (I-8-g) shown above in    which A, B, D, L, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, R⁶, R⁷, W, X and Y have    the abovementioned meanings are obtained when compounds of the    formulae (I-1-a) to (I-8-a) shown above in which A, B, D, Q¹, Q²,    Q³, Q⁴, Q⁵, Q⁶, W, X and Y have the abovementioned meanings are    reacted in each case

-   (α) with isocyanates or isothiocyanates of the formula (XXI)

R⁶—N═C=L

-   -   in which    -   R⁶ and L have the abovementioned meanings,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of a catalyst, or

-   ( ) with carbamoyl chlorides or thiocarbamoyl chlorides of the    formula (XXII)

-   -   in which    -   L, R⁶ and R⁷ have the abovementioned meanings,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid-binding agent,    -   (P) that compounds of the formulae (I-1-a) to (I-8-a) shown        above in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, W, X and Y have        the abovementioned meanings are obtained when compounds of the        formulae (I-1-a′) to (I-8-a′) in which A, B, D, Q¹, Q², Q³, Q⁴,        Q⁵, Q⁶, X and Y have the abovementioned meanings and W′        preferably represents bromine

-   -   are reacted with alcohols of the formula

W—OH

-   -   in which    -   W has the abovementioned meaning,        -   if appropriate in the presence of a diluent, a Cu(I) salt            (for example CuBr, CuI) and a strong base (for example            sodium hydride, potassium tert-butoxide).

Furthermore, it has been found that the new compounds of the formula (I)have a very good activity as pesticides, preferably as insecticides,acaricides and/or herbicides.

Surprisingly, it has now also been found that certain substituted cyclicketoenols, when used jointly with the compounds which improve crop planttolerance (safeners/antidotes) described hereinbelow, are extremelyeffective in preventing damage of the crop plants and can be usedespecially advantageously as combination products with a broad range ofactivity for the selective control of undesired plants in crops ofuseful plants, such as, for example, in cereals, but also in maize,soybeans and rice.

The invention also relates to selectively herbicidal compositions withan effective content of an active compound combination comprising, ascomponents,

-   (a′) at least one substituted cyclic ketoenol of the formula (I) in    which CKE, W, X and Y have the abovementioned meanings    and-   (b′) at least one compound which improves crop plant tolerance and    which is selected from the following group of compounds:    4-dichloroacetyl-1-oxa-4-aza-spiro[4.5]-decane (AD-67, MON-4660),    1-dichloroacetyl-hexahydro-3,3,8a-trimethylpyrrolo[1,2-a]-pyrimidin-6(2H)-one    (dicyclonon, BAS-145138),    4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine    (benoxacor), 1-methyl-hexyl 5-chloro-quinolin-8-oxy-acetate    (cloquintocet-mexyl-cf. also related compounds in EP-A-86750,    EP-A-94349, EP-A-191736, EP-A-492366),    3-(2-chloro-benzyl)-1-(1-methyl-1-phenyl-ethyl)-urea (cumyluron),    α-(cyanomethoximino)-phenylacetonitrile (cyometrinil),    2,4-dichloro-phenoxyacetic acid (2,4-D),    4-(2,4-dichloro-phenoxy)-butyric acid (2,4-DB),    1-(1-methyl-1-phenyl-ethyl)-3-(4-methyl-phenyl)-urea (daimuron,    dymron), 3,6-dichloro-2-methoxy-benzoic acid (dicamba),    S-1-methyl-1-phenyl-ethyl piperidine-1-thiocarboxylate    (dimepiperate),    2,2-dichloro-N-(2-oxo-2-(2-propenylamino)-ethyl)-N-(2-propenyl)-acetamide    (DKA-24), 2,2-dichloro-N,N-di-2-propenyl acetamide (dichlormid),    4,6-dichloro-2-phenyl-pyrimidine (fenclorim), ethyl    1-(2,4-dichloro-phenyl)-5-trichloro-methyl-1H-1,2,4-triazole-3-carboxylate    (fenchlorazole-ethyl—cf. also related compounds in EP-A-174562 and    EP-A-346620), phenyl-methyl    2-chloro-4-trifluoromethyl-thiazole-5-carboxylate (flurazole),    4-chloro-N-(1,3-dioxolan-2-yl-methoxy)-α-trifluoro-acetophenone    oxime (fluxofenim),    3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyl-oxazolidine (furilazole,    MON-13900), ethyl 4,5-dihydro-5,5-diphenyl-3-isoxazole-carboxylate    (isoxadifen-ethyl—cf. also related compounds in WO-A-95/07897),    1-(ethoxycarbonyl)-ethyl-3,6-dichloro-2-methoxybenzoate    (lactidichlor), (4-chloro-o-tolyloxy)-acetic acid (MCPA),    2-(4-chloro-o-tolyloxy)-propionic acid (mecoprop), diethyl    1-(2,4-dichloro-phenyl)-4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylate    (mefenpyr-diethyl—cf. also related compounds in WO-A-91/07874),    2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),    2-propenyl-1-oxa-4-azaspiro[4.5]decane 4-carbodithioate (MG-838),    1,8-naphthalic anhydride,    α-(1,3-dioxolan-2-yl-methoximino)-phenylacetonitrile (oxabetrinil),    2,2-dichloro-N-(1,3-dioxolan-2-yl-methyl)-N-(2-propenyl)-acetamide    (PPG-1292), 3-dichloroacetyl-2,2-dimethyl-oxazolidine (R-28725),    3-dichloroacetyl-2,2,5-trimethyl-oxazolidine (R-29148),    4-(4-chloro-o-tolyl)-butyric acid, 4-(4-chloro-phenoxy)-butyric    acid, diphenylmethoxyacetic acid, methyl diphenylmethoxyacetate,    ethyl diphenylmethoxyacetate, methyl    1-(2-chloro-phenyl)-5-phenyl-1H-pyrazole-3-carboxylate, ethyl    1-(2,4-dichloro-phenyl)-5-methyl-1H-pyrazole-3-carboxylate, ethyl    1-(2,4-dichloro-phenyl)-5-isopropyl-1H-pyrazole-3-carboxylate, ethyl    1-(2,4-dichloro-phenyl)-5-(1,1-dimethyl-ethyl)-1H-pyrazole-3-carboxylate,    ethyl 1-(2,4-dichloro-phenyl)-5-phenyl-1H-pyrazole-3-carboxylate    (cf. also related compounds in EP-A-269806 and EP-A-333131), ethyl    5-(2,4-dichloro-benzyl)-2-isoxazoline-3-carboxylate, ethyl    5-phenyl-2-isoxazoline-3-carboxylate, ethyl    5-(4-fluoro-phenyl)-5-phenyl-2-isoxazoline-3-carboxylate (cf. also    related compounds in WO-A-91/08202), 1,3-dimethyl-but-1-yl    5-chloro-quinolin-8-oxy-acetate, 4-allyloxy-butyl    5-chloro-quinolin-8-oxy-acetate, 1-allyloxy-prop-2-yl    5-chloro-quinolin-8-oxy-acetate, methyl    5-chloro-quinolin-8-oxy-acetate, ethyl    5-chloro-quinolin-8-oxy-acetate, allyl    5-chloro-quinoxalin-8-oxy-acetate, 2-oxo-prop-1-yl    5-chloro-quinolin-8-oxy-acetate, diethyl    5-chloro-quinolin-8-oxy-malonate, diallyl    5-chloro-quinoxalin-8-oxy-malonate, diethyl    5-chloro-quinolin-8-oxy-malonate (cf. also related compounds in    EP-A-582198), 4-carboxy-chroman-4-yl-acetic acid (AC-304415, cf.    EP-A-613618), 4-chloro-phenoxy-acetic acid,    3,3′-dimethyl-4-methoxy-benzophenone,    1-bromo-4-chloromethylsulphonyl-benzene,    1-[4-(N-2-methoxybenzoylsulphamoyl)-phenyl]-3-methyl-urea (alias    N-(2-methoxy-benzoyl)-4-[(methylamino-carbonyl)-amino]-benzenesulphonamide),    1-[4-(N-2-methoxybenzoylsulphamoyl)-phenyl]-3,3-dimethyl-urea,    1-[4-(N-4,5-dimethylbenzoylsulphamoyl)-phenyl]-3-methyl-urea,    1-[4-(N-naphthylsulphamoyl)-phenyl]-3,3-dimethyl-urea,    N-(2-methoxy-5-methyl-benzoyl)-4-(cyclopropyl-aminocarbonyl)-benzenesulphonamide,    and/or one of the following compounds (defined by general formulae)    of the general formula (IIa)

or of the general formula (IIb)

or of the formula (IIc)

where

-   n represents a number of between 0 and 5,-   A¹ represents one of the divalent heterocyclic groups outlined    hereinbelow

-   n represents a number of between 0 and 5,-   A² represents alkanediyl having 1 or 2 carbon atoms which is    optionally substituted by C₁-C₄-alkyl and/or C₁-C₄-alkoxycarbonyl,-   R¹⁴ represents hydroxyl, mercapto, amino, C₁-C₆-alkoxy,    C₁-C₆-alkylthio, C₁-C₆-alkylamino or di(C₁-C₄-alkylamino,-   R¹⁵ represents hydroxyl, mercapto, amino, C₁-C₆-alkoxy,    C₁-C₆-alkylthio, C₁-C₆-alkylamino or di(C₁-C₄-alkyl)amino,-   R¹⁶ represents C₁-C₄-alkyl which is optionally substituted in each    case by fluorine, chlorine and/or bromine,-   R¹⁷ represents hydrogen, or represents C₁-C₆-alkyl, C₂-C₆-alkenyl or    C₂-C₆-alkinyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, dioxolanyl-C₁-C₄-alkyl,    furyl, furyl-C₁-C₄-alkyl, thienyl, thiazolyl, piperidinyl, each of    which is optionally substituted by fluorine, chlorine and/or    bromine, or represents phenyl which is optionally Substituted by    fluorine, chlorine and/or bromine or C₁-C₄-alkyl,-   R¹⁸ represents hydrogen, or represents C₁-C₆-alkyl, C₂-C₆-alkenyl or    C₂-C₆-alkinyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, dioxolanyl-C₁-C₄-alkyl,    furyl, furyl-C₁-C₄-alkyl, thienyl, thiazolyl, piperidinyl, each of    which is optionally substituted by fluorine, chlorine and/or    bromine, or represents phenyl which is optionally substituted by    fluorine, chlorine and/or bromine or C₁-C₄-alkyl, or together with    R¹⁷ represents C₃-C₆-alkanediyl or C₂-C₅-oxaalkanediyl, each of    which is optionally substituted by C₁-C₄-alkyl, phenyl, furyl, a    fused benzene ring or by two substituents which, together with the C    atom to which they are bonded, form a 5- or 6-membered carbocycle,-   R¹⁹ represents hydrogen, cyano, halogen, or represents C₁-C₄-alkyl,    C₃-C₆-cycloalkyl or phenyl, each of which is optionally substituted    by fluorine, chlorine and/or bromine,-   R²⁰ represents hydrogen, or represents C₁-C₆-alkyl, C₃-C₆-cycloalkyl    or tri(C₁-C₄-alkyl)silyl, in each case optionally substituted by    hydroxyl, cyano, halogen or C₁-C₄-alkoxy,-   R²¹ represents hydrogen, cyano, halogen, or represents C₁-C₄-alkyl,    C₃-C₆-cycloalkyl or phenyl, each of which is optionally substituted    by fluorine, chlorine and/or bromine,-   X¹ represents nitro, cyano, halogen, C₁-C₄-alkyl,    C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy or C₁-C₄-halogenoalkoxy,-   X² represents hydrogen, cyano, nitro, C₁-C₄-alkyl,    C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy or C₁-C₄-halogenoalkoxy,-   X³ represents hydrogen, cyano, nitro, C₁-C₄-alkyl,    C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy or C₁-C₄-halogenoalkoxy,    and/or the following compounds (defined by general formulae)    of the general formula (IId)

or of the general formula (IIe)

where

-   n represents a number of between 0 and 5,-   R²² represents hydrogen or C₁-C₄-alkyl,-   R²³ represents hydrogen or C₁-C₄-alkyl,-   R²⁴ represents hydrogen, or represents C₁-C₆-alkyl, C₁-C₆-alkoxy,    C₁-C₆-alkylthio, C₁-C₆-alkylamino or di(C₁-C₄-alkyl)amino, each of    which is optionally substituted by cyano, halogen or C₁-C₄-alkoxy,    or represents C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyloxy,    C₃-C₆-cycloalkylthio or C₃-C₆-cycloalkylamino, each of which is    optionally substituted by cyano, halogen or C₁-C₄-alkyl,-   R²⁵ represents hydrogen, or represents C₁-C₆-alkyl which is    optionally substituted by cyano, hydroxyl, halogen or C₁-C₄-alkoxy,    or represents C₃-C₆-alkenyl or C₃-C₆-alkinyl, each of which is    optionally substituted by cyano or halogen, or represents    C₃-C₆-cycloalkyl which is optionally substituted by cyano, halogen    or C₁-C₄-alkyl,-   R²⁶ represents hydrogen, or represents C₁-C₆-alkyl which is    optionally substituted by cyano, hydroxyl, halogen or C₁-C₄-alkoxy,    or represents C₃-C₆-alkenyl or C₃-C₆-alkinyl, each of which is    optionally substituted by cyano or halogen, or represents    C₃-C₆-cycloalkyl which is optionally substituted by cyano, halogen    or C₁-C₄-alkyl, or represents phenyl which is optionally substituted    by nitro, cyano, halogen, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl,    C₁-C₄-alkoxy or C₁-C₄-halogenoalkoxy, or together with R²⁵    represents C₂-C₆-alkanediyl or C₂-C₅-oxaalkanediyl, each of which is    optionally substituted by C₁-C₄-alkyl,-   X⁴ represents nitro, cyano, carboxyl, carbamoyl, formyl, sulphamoyl,    hydroxyl, amino, halogen, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl,    C₁-C₄-alkoxy or C₁-C₄-halogenoalkoxy, and-   X⁵ represents nitro, cyano, carboxyl, carbamoyl, formyl, sulphamoyl,    hydroxyl, amino, halogen, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl,    C₁-C₄-alkoxy or C₁-C₄-halogenoalkoxy.

Formula (I) provides a general definition of the compounds according tothe invention. Preferred substituents or ranges of the radicals given inthe formulae mentioned hereinabove and hereinbelow are illustrated inthe following text:

-   W preferably represents C₁-C₆-alkoxy, C₁-C₆-halogenoalkoxy,    C₁-C₄-alkoxy-C₂-C₄-alkyloxy, C₁-C₄-alkoxy-bis-C₂-C₄-alkyloxy, or    represents C₃-C₆-cycloalkyl-C₁-C₃-alkanediyloxy which is optionally    monosubstituted to trisubstituted by fluorine, chlorine, C₁-C₃-alkyl    or C₁-C₃-alkoxy and in which one methylene group of the ring can    optionally be interrupted by oxygen or sulphur,-   X preferably represents C₁-C₆-alkyl,-   Y preferably represents chlorine, bromine or iodine,-   CKE preferably represents one of the groups

-   A preferably represents hydrogen, or represents C₁-C₁₂-alkyl,    C₃-C₈-alkenyl, C₁-C₁₀-alkoxy-C₁-C₈-alkyl or    C₁-C₁₀-alkylthio-C₁-C₆-alkyl, each of which is optionally    substituted by halogen, or represents C₃-C₈-cycloalkyl in which one    or two ring members which are not directly adjacent are optionally    replaced by oxygen and/or sulphur and which is optionally    substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy, or represents    phenyl, naphthyl, hetaryl having 5 to 6 ring atoms (for example    furanyl, pyridyl, imidazolyl, triazolyl, pyrazolyl, pyrimidyl,    thiazolyl or thienyl), phenyl-C₁-C₆-alkyl or naphthyl-C₁-C₆-alkyl,    each of which is optionally substituted by halogen, C₁-C₆-alkyl,    C₁-C₆-halogenoalkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkoxy, cyano or    nitro,-   B preferably represents hydrogen, C₁-C₁₂-alkyl or    C₁-C₈-alkoxy-C₁-C₆-alkyl, or-   A, B and the carbon atom to which they are bonded preferably    represent saturated C₃-C₁₀-cycloalkyl or unsaturated    C₅-C₁₀-cycloalkyl in which one ring member is optionally replaced by    oxygen or sulphur and which is optionally monosubstituted or    disubstituted by C₁-C₈-alkyl, C₃-C₁₀-cycloalkyl,    C₁-C₈-halogenoalkyl, C₁-C₈-alkoxy, C₁-C₈-alkylthio, halogen or    phenyl, or-   A, B and the carbon atom to which they are bonded preferably    represent C₃-C₆-cycloalkyl which is substituted by an alkylenediyl    group which is optionally substituted by C₁-C₄-alkyl and which    optionally contains one or two oxygen and/or sulphur atoms which are    not directly adjacent, or by an alkylenedioxy or by an    alkylenedithio group, this group together with the carbon atom to    which it is bonded forming a further five- to eight-membered ring,    or-   A, B and the carbon atom to which they are bonded preferably    represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl in which two    substituents together with the carbon atoms to which they are bonded    represent C₂-C₆-alkanediyl, C₂-C₆-alkenediyl or    C₄-C₆-alkanedienediyl, in which one methylene group is optionally    replaced by oxygen or sulphur and each of which is optionally    substituted by C₁-C₆-alkyl, C₁-C₆-alkoxy or halogen,-   D preferably represents hydrogen, or represents C₁-C₁₂-alkyl,    C₃-C₈-alkenyl, C₃-C₈-alkinyl, C₁-C₁₀-alkoxy-C₂-C₈-alkyl, each of    which is optionally substituted by halogen, or represents    C₃-C₈-cycloalkyl in which a ring member is optionally replaced by    oxygen or sulphur and which is optionally substituted by halogen,    C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-halogenoalkyl, or represents    phenyl, hetaryl having 5 or 6 ring atoms (for example furanyl,    imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl,    thienyl or triazolyl), phenyl-C₁-C₆-alkyl or hetaryl-C₁-C₆-alkyl    having 5 or 6 ring atoms (for example furanyl, imidazolyl, pyridyl,    thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl or triazolyl),    each of which is optionally substituted by halogen, C₁-C₆-alkyl,    C₁-C₆-halogenoalkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkoxy, cyano or    nitro, or-   A and D together preferably represent in each case optionally    substituted C₃-C₆-alkanediyl or C₃-C₆-alkenediyl, in which one    methylene group is optionally replaced by a carbonyl group, oxygen    or sulphur, and    -   where suitable substituents in each case are:    -   halogen, hydroxyl, mercapto, or C₁-C₁₀-alkyl, C₁-C₆-alkoxy,        C₁-C₆-alkylthio, C₃-C₇-cycloalkyl, phenyl or benzyloxy, each of        which is optionally substituted by halogen; or a further        C₃-C₆-alkanediyl group, C₃-C₆-alkenediyl group or a butadienyl        group which is optionally substituted by C₁-C₆-alkyl or in which        two adjacent substituents together with the carbon atoms to        which they are bonded optionally form a further saturated or        unsaturated cycle having 5 or 6 ring atoms (in the case of the        compound of the formula (I-1), A and D will now jointly with the        atoms to which they are bonded represent for example the groups        AD-1 to AD-10, which are detailed further below) which can        contain oxygen or sulphur, or which optionally contains one of        the following groups

-   -   or

-   A and Q¹ jointly preferably represent C₃-C₆-alkanediyl or    C₄-C₆-alkenediyl, each of which is optionally monosubstituted or    disubstituted by identical or different substituents from the series    consisting of halogen, hydroxyl, or C₁-C₁₀-alkyl, C₁-C₆-alkoxy,    C₁-C₆-alkylthio, C₃-C₇-cycloalkyl, each of which is optionally    monosubstituted to trisubstituted by identical or different halogen    substituents, or benzyloxy or phenyl, each of which is optionally    monosubstituted to trisubstituted by identical or different    substituents from the series consisting of halogen, C₁-C₆-alkyl or    C₁-C₆-alkoxy, this C₃-C₆-alkanediyl or C₄-C₆-alkenediyl additionally    optionally containing one of the following groups

-   -   or being bridged via a C₁-C₂-alkanediyl group or by an oxygen        atom, or

-   Q¹ preferably represents hydrogen or C₁-C₄-alkyl,

-   Q², Q⁴, Q⁵ and Q⁶ independently of one another preferably represent    hydrogen or C₁-C₄-alkyl,

-   Q³ preferably represents hydrogen, C₁-C₆-alkyl,    C₁-C₆-alkoxy-C₁-C₂-alkyl, C₁-C₆-alkylthio-C₁-C₂-alkyl,    C₃-C₈-cycloalkyl which is optionally substituted by C₁-C₄-alkyl or    C₁-C₄-alkoxy and in which one methylene group is optionally replaced    by oxygen or sulphur, or phenyl which is optionally substituted by    halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,    C₁-C₂-halogenoalkoxy, cyano or nitro, or

-   Q³ and Q⁴ together with the carbon atom to which they are bonded    preferably represent a C₃-C₇ ring which is optionally substituted by    C₁-C_(a)-alkyl, C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl and in which one    ring member is optionally replaced by oxygen or sulphur,

-   G preferably represents hydrogen (a) or one of the groups

in particular (a), (b), (c) or (g), in which

-   -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur.

-   R¹ preferably represents C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,    C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl or    poly-C₁-C₈-alkoxy-C₁-C₈-alkyl, each of which is optionally    substituted by halogen, or represents C₃-C₈-cycloalkyl in which one    or more (preferably not more than two) ring members which are not    directly adjacent are optionally replaced by oxygen and/or sulphur    and which is optionally substituted by halogen, C₁-C₆-alkyl or    C₁-C₆-alkoxy,    -   or phenyl which is optionally substituted by halogen, cyano,        nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl,        C₁-C₆-halogenoalkoxy, C₁-C₆-alkylthio or C₁-C₆-alkylsulphonyl,    -   or phenyl-C₁-C₆-alkyl which is optionally substituted by        halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy,        C₁-C₆-halogenoalkyl or C₁-C₆-halogenoalkoxy,    -   or 5- or 6-membered hetaryl (for example pyrazolyl, thiazolyl,        pyridyl, pyrimidyl, furanyl or thienyl) which is optionally        substituted by halogen or C₁-C₆-alkyl,    -   or phenoxy-C₁-C₆-alkyl which is optionally substituted by        halogen or C₁-C₆-alkyl, or    -   5- or 6-membered hetaryloxy-C₁-C₆-alkyl (for example        pyridyloxy-C₁-C₆-alkyl, pyrimidyloxy-C₁-C₆-alkyl or        thiazolyloxy-C₁-C₆-alkyl) which is optionally substituted by        halogen, amino or C₁-C₆-alkyl.

-   R² preferably represents C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,    C₁-C₈-alkoxy-C₂-C₈-alkyl or poly-C₁-C₈-alkoxy-C₂-C₈-alkyl, each of    which is optionally substituted by halogen,    -   or C₃-C₈-cycloalkyl which is optionally substituted by halogen,        C₁-C₆-alkyl or C₁-C₆-alkoxy, or    -   phenyl or benzyl, each of which is optionally substituted by        halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy,        C₁-C₆-halogenoalkyl or C₁-C₆-halogenoalkoxy,

-   R³ preferably represents C₁-C₈-alkyl which is optionally substituted    by halogen, or phenyl or benzyl, each of which is optionally    substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,    C₁-C_(a)-halogenoalkyl, C₁-C_(a)-halogenoalkoxy, cyano or nitro,

-   R⁴ and R⁵ preferably independently of one another represent    C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylamino, di-(C₁-C₈-alkyl)amino,    C₁-C₈-alkylthio, C₂-C₈-alkenylthio or C₃-C₇-cycloalkylthio, each of    which is optionally substituted by halogen, or phenyl, phenoxy or    phenylthio, each of which is optionally substituted by halogen,    nitro, cyano, C₁-C₄-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-alkylthio,    C₁-C₄-halogenoalkylthio, C₁-C₄-alkyl or C₁-C₄-halogenoalkyl,

-   R⁶ and R⁷ independently of one another preferably represent    hydrogen, or C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₈-alkoxy,    C₃-C₈-alkenyl or C₁-C₈-alkoxy-C₁-C₈-alkyl, each of which is    optionally substituted by halogen, or phenyl which is optionally    substituted by halogen, C₁-C₈-halogenoalkyl, C₁-C₈-alkyl or    C₁-C₈-alkoxy, or benzyl which is optionally substituted by halogen,    C₁-C₈-alkyl, C₁-C₈-halogenoalkyl or C₁-C₈-alkoxy, or together    represent a C₃-C₆-alkylene radical which is optionally substituted    by C₁-C₄-alkyl and in which one carbon atom is optionally replaced    by oxygen or sulphur,

-   R¹³ preferably represents hydrogen, C₁-C₈-alkyl or C₁-C₈-alkoxy,    each of which is optionally substituted by halogen, C₃-C₈-cycloalkyl    in which one methylene group is optionally replaced by oxygen or    sulphur and which is optionally substituted by halogen, C₁-C₄-alkyl    or C₁-C₄-alkoxy, or phenyl, phenyl-C₁-C₄-alkyl or    phenyl-C₁-C₄-alkoxy, each of which is optionally substituted by    halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl,    C₁-C₄-halogenoalkoxy, nitro or cyano,

-   R^(14a) preferably represents hydrogen or C₁-C₈-alkyl, or

-   R¹³ and R^(14a) together preferably represent C₄-C₆-alkanediyl,

-   R^(15a) and R^(16a) are identical or different and preferably    represent C₁-C₆-alkyl, or

-   R^(15a) and R^(16a) together preferably represent a C₂-C₄-alkanediyl    radical which is optionally substituted by C₁-C₆-alkyl,    C₁-C₆-halogenoalkyl or by phenyl which is optionally substituted by    halogen, C₁-C₆-alkyl, C₁-C₄-halogenoalkyl, C₁-C₆-alkoxy,    C₁-C₄-halogenoalkoxy, nitro or cyano,

-   R^(17a) and R^(18a) independently of one another preferably    represent hydrogen, C₁-C₈-alkyl which is optionally substituted by    halogen, or phenyl which is optionally substituted by halogen,    C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl,    C₁-C₄-halogenoalkoxy, nitro or cyano, or

-   R^(17a) and R^(18a) together with the carbon atom to which they are    bonded preferably represent a carbonyl group or C₅-C₇-cycloalkyl in    which one methylene group is optionally replaced by oxygen or    sulphur and which is optionally substituted by halogen, C₁-C₄-alkyl    or C₁-C₄-alkoxy.

-   R^(19a) and R^(20a) independently of one another preferably    represent C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₁-C₁₀-alkoxy,    C₁-C₁₀-alkylamino, C₃-C₁₀-alkenylamino, di-(C₁-C₁₀-alkyl)amino or    di-(C₃-C₁₀-alkenyl)amino.

In the definitions of radicals which have been mentioned as beingpreferred, halogen represents fluorine, chlorine, bromine and iodine, inparticular fluorine, chlorine and bromine.

-   W especially preferably represents C₁-C₄-alkoxy,    C₁-C₄-halogenoalkoxy, C₁-C₃-alkoxy-C₂-C₃-alkyloxy,    C₁-C₂-alkoxy-bis-C₂-C₃-alkyloxy or    C₃-C₆-cycloalkyl-C₁-C₂-alkanediyloxy in which one methylene group of    the ring can optionally be interrupted by oxygen,-   X especially preferably represents C₁-C₃-alkyl,-   Y especially preferably represents chlorine or bromine,-   CKE especially preferably represents one of the groups

-   A especially preferably represents hydrogen, or represents    C₁-C₆-alkyl, alkoxy-C₁-C₂-alkyl, each of which is optionally    monosubstituted to trisubstituted by fluorine or chlorine, or    represents C₃-C₆-cycloalkyl which is optionally monosubstituted or    disubstituted by C₁-C₂-alkyl or C₁-C₂-alkoxy, or (but not in the    case of the compounds of formulae (I-3), (I-4), (I-6) and (I-7))    represents phenyl or benzyl, each of which is optionally    monosubstituted or disubstituted by fluorine, chlorine, bromine,    C₁-C₄-alkyl, C₁-C₂-halogenoalkyl, C₁-C₄-alkoxy,    C₁-C₂-halogenoalkoxy, cyano or nitro,-   B especially preferably represents hydrogen, C₁-C₄-alkyl or    C₁-C₂-alkoxy-C₁-C₂-alkyl, or-   A, B and the carbon atom to which they are bonded especially    preferably represent saturated or unsaturated C₅-C₇-cycloalkyl in    which one ring member is optionally replaced by oxygen or sulphur    and which is optionally monosubstituted or disubstituted by    C₁-C₆-alkyl, trifluoromethyl or C₁-C₆-alkoxy, with the proviso that,    in this case, Q³ especially preferably represents hydrogen or    methyl, or-   A, B and the carbon atom to which they are bonded especially    preferably represent C₅-C₆-cycloalkyl which is optionally    substituted by an alkylenediyl group which optionally contains one    or two oxygen or sulphur atoms which are not directly adjacent to    each other and is optionally substituted by methyl or ethyl, or by    an alkylenedioxyl or by an alkylenedithiol group, which group,    together with the carbon atom to which it is bonded, forms a further    five- or six-membered ring, with the proviso that, in this case, Q³    especially preferably represents hydrogen or methyl,-   A, B and the carbon atom to which they are bonded especially    preferably represent C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in which    two substituents together with the carbon atoms to which they are    bonded represent C₂-C₄-alkanediyl, C₂-C₄-alkenediyl or    butandienediyl, each of which is optionally substituted by    C₁-C₂-alkyl or C₁-C₂-alkoxy, with the proviso that, in this case, Q³    especially preferably represents hydrogen or methyl,-   D especially preferably represents hydrogen, or represents    C₁-C₆-alkyl, C₃-C₆-alkenyl, C₁-C₄-alkoxy-C₂-C₃-alkyl, each of which    is optionally monosubstituted to trisubstituted by fluorine, or    represents C₃-C₆-cycloalkyl which is optionally monosubstituted or    disubstituted by C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl    and in which one methylene group is optionally replaced by oxygen,    or (but not in the case of the compounds of the formulae (I-1))    represents phenyl or pyridyl, each of which is optionally    monosubstituted or disubstituted by fluorine, chlorine, bromine,    C₁-C₄-alkyl, C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy or    C₁-C₄-halogenoalkoxy, or-   A and D jointly especially preferably represent C₃-C₅-alkanediyl    which is optionally monosubstituted or disubstituted and in which    one methylene group can be replaced by a carbonyl group (but not in    the case of the compounds of the formula (I-1)), oxygen or sulphur,    with C₁-C₂-alkyl or C₁-C₂-alkoxy being suitable substituents, or-   A and D (in the case of the compounds of the formula (I-1)) together    with the atoms to which they are bonded represent one of the groups    AD-1 to AD-10

-   -   or

-   A and Q¹ together especially preferably represent C₃-C₄-alkanediyl,    in each case optionally monosubstituted or disubstituted by    identical or different substituents from the series consisting of    C₁-C₂-alkyl or C₁-C₂-alkoxy, or

-   Q¹ especially preferably represents hydrogen,

-   Q² especially preferably represents hydrogen,

-   Q⁴, Q⁵ and Q⁶ especially preferably independently of one another    represent hydrogen or C₁-C₃-alkyl,

-   Q³ especially preferably represents hydrogen, C₁-C₄-alkyl or    C₃-C₆-cycloalkyl which is optionally monosubstituted or    disubstituted by methyl or methoxy, or

-   Q³ and Q⁴ especially preferably together with the carbon atom to    which they are bonded represent a saturated C₅-C₆ ring which is    optionally substituted by C₁-C₂-alkyl or C₁-C₂-alkoxy and in which    one ring member is optionally replaced by oxygen or sulphur, with    the proviso that, in this case, A especially preferably represents    hydrogen or methyl, or

-   G especially preferably represents hydrogen (a) or one of the groups

in particular (a), (b) or (c),

-   -   in which    -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur.

-   R¹ especially preferably represents C₁-C₈-alkyl, C₂-C₁₈-alkenyl,    C₁-C₄-alkoxy-C₁-C₂-alkyl, C₁-C₄-alkylthio-C₁-C₂-alkyl, each of which    is optionally monosubstituted to trisubstituted by fluorine or    chlorine, or represents C₃-C₆-cycloalkyl which is optionally    monosubstituted or disubstituted by fluorine, chlorine, C₁-C₂-alkyl    or C₁-C₂-alkoxy and in which one or two ring members which are not    directly adjacent are optionally replaced by oxygen,    -   or represent phenyl which is optionally monosubstituted or        disubstituted by fluorine, chlorine, bromine, cyano, nitro,        C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl or        C₁-C₂-halogenoalkoxy,

-   R² especially preferably represents C₁-C₈-alkyl, C₂-C₈-alkenyl or    C₁-C₄-alkoxy-C₂-C₄-alkyl, each of which is optionally    monosubstituted to trisubstituted by fluorine, or    -   represents C₃-C₆-cycloalkyl which is optionally substituted by        C₁-C₂-alkyl or C₁-C₂-alkoxy, or    -   represents phenyl or benzyl, each of which is optionally        monosubstituted or disubstituted by fluorine, chlorine, bromine,        cyano, nitro, C₁-C₄-alkyl, C₁-C₃-alkoxy, trifluoromethyl or        trifluoromethoxy,

-   R³ especially preferably represents C₁-C₆-alkyl which is optionally    monosubstituted to trisubstituted by fluorine, or represents phenyl    which is optionally in each case monosubstituted by fluorine,    chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, trifluoromethyl,    trifluoromethoxy, cyano or nitro,

-   R⁴ especially preferably represents C₁-C₆-alkyl, C₁-C₆-alkoxy,    C₁-C₆-alkylamino, di-(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio,    C₃-C₆-alkenylthio, C₃-C₆-cycloalkylthio, or represents phenyl,    phenoxy or phenylthio, each of which is optionally monosubstituted    by fluorine, chlorine, bromine, nitro, cyano, C₁-C₃-alkoxy,    C₁-C₃-halogenoalkoxy, C₁-C₃-alkylthio, C₁-C₃-halogenoalkylthio,    C₁-C₃-alkyl or trifluoromethyl,

-   R⁵ especially preferably represents C₁-C₆-alkoxy or C₁-C₆-alkylthio,

-   R⁶ especially preferably represents hydrogen, C₁-C₆-alkyl,    C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₃-C₆-alkenyl,    C₁-C₆-alkoxy-C₁-C₄-alkyl, or represents phenyl which is optionally    monosubstituted by fluorine, chlorine, bromine, trifluoromethyl,    C₁-C₄-alkyl or C₁-C₄-alkoxy, or represents benzyl which is    optionally monosubstituted by fluorine, chlorine, bromine,    C₁-C₄-alkyl, trifluoromethyl or C₁-C₄alkoxy,

-   R⁷ especially preferably represents C₁-C₆-alkyl, C₃-C₆-alkenyl or    C₁-C₆-alkoxy-C₁-C₄-alkyl,

-   R⁶ and R⁷ together especially preferably represent a C₄-C₅-alkylene    radical which is optionally substituted by methyl or ethyl and in    which one methylene group is optionally replaced by oxygen or    sulphur.

In the definitions of radicals mentioned as being especially preferred,halogen represents fluorine, chlorine and bromine, in particularfluorine and chlorine.

-   W very especially preferably represents methoxy, ethoxy, n-propoxy,    iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, methoxy-ethyloxy,    ethoxy-ethyloxy, cyclopropyl-methoxy, cyclopentyl-methoxy or    cyclohexyl-methoxy,-   X very especially preferably represents methyl or ethyl,-   Y very especially preferably represents chlorine or bromine,-   CKE very particularly preferably represents one of the groups

-   A very especially preferably represents hydrogen, or represents    C₁-C₄-alkyl or C₁-C₂-alkoxy-C₁-C₂-alkyl, each of which is    monosubstituted to trisubstituted by fluorine, or represents    cyclopropyl, cyclopentyl or cyclohexyl, and only in the case of the    compounds of the formula (I-5) represents phenyl which is optionally    in each case substituted by fluorine, chlorine, bromine, methyl,    ethyl, n-propyl, iso-propyl, methoxy, ethoxy, trifluoromethyl,    trifluoromethoxy, cyano or nitro,-   B very especially preferably represents hydrogen, methyl or ethyl,    or-   A, B and the carbon atom to which they are bonded very especially    preferably represent saturated C₅-C₆-cycloalkyl in which one ring    member is optionally replaced by oxygen or sulphur and which is    optionally monosubstituted by methyl, ethyl, propyl, isopropyl,    trifluoromethyl, methoxy, ethoxy, propoxy or butoxy, with the    proviso that, in this case, Q³ very especially preferably represents    hydrogen, or-   A, B and the carbon atom to which they are bonded very especially    preferably represent C₆-cycloalkyl which is optionally substituted    by an alkylenedioxyl group containing two oxygen atoms which are not    directly adjacent, with the proviso that, in this case, Q³ very    especially preferably represents hydrogen, or-   A, B and the carbon atom to which they are bonded very especially    preferably represent C₅-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in which    two substituents together with the carbon atoms to which they are    bonded represent C₂-C₄-alkanediyl or C₂-C₄-alkenediyl or    butadienediyl, with the proviso that, in this case, Q³ very    especially preferably represents hydrogen,-   D very especially preferably represents hydrogen, or represents    C₁-C₄-alkyl, C₃-C₄-alkenyl, C₁-C₄-alkoxy-C₂-C₃-alkyl, each of which    is optionally monosubstituted to trisubstituted by fluorine, or    represents cyclopropyl, cyclopentyl or cyclohexyl, or (but not in    the case of compounds of the formulae (I-1)) represents phenyl or    pyridyl, each of which is optionally monosubstituted by fluorine,    chlorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy or    trifluoromethyl,    or-   A and D together very especially preferably represent    C₃-C₅-alkanediyl which is optionally monosubstituted by methyl or    methoxy and in which one carbon atom is optionally replaced by    oxygen or sulphur, or represent the group AD-1-   A and Q¹ together very especially preferably represent    C₃-C₄-alkanediyl which is optionally monosubstituted or    disubstituted by methyl or methoxy or-   Q¹ very especially preferably represents hydrogen,-   Q² very especially preferably represents hydrogen,-   Q⁴, Q⁵ and Q⁶ very especially preferably independently of one    another represent hydrogen or methyl,-   Q³ very especially preferably represents hydrogen, methyl, ethyl or    propyl, or-   Q³ and Q⁴ together with the carbon atom to which they are bonded    very especially preferably represent a saturated C₅-C₆ ring which is    optionally monosubstituted by methyl or methoxy, with the proviso    that, in this case, A very especially preferably represents    hydrogen,-   G very especially preferably represents hydrogen (a) or one of the    groups

-   -   in which    -   L represents oxygen or sulphur,    -   M represents oxygen or sulphur and    -   E represents an ammonium ion,

-   R¹ very especially preferably represents C₁-C₆-alkyl,    C₂-C₁₇-alkenyl, C₁-C₂-alkoxy-C₁-alkyl, C₁-C₂-alkylthio-C₁-alkyl or    represents cyclopropyl or cyclohexyl, each of which is optionally    monosubstituted by fluorine, chlorine, methyl or methoxy,    -   or represents phenyl which is optionally monosubstituted by        fluorine, chlorine, bromine, cyano, nitro, methyl, methoxy,        trifluoromethyl or trifluoromethoxy,

-   R² very especially preferably represents C₁-C₈-alkyl, C₂-C₆-alkenyl    or C₁-C₄-alkoxy-C₂-C₃-alkyl, phenyl or benzyl, each of which is    optionally monosubstituted by fluorine,

-   R³ very especially preferably represents C₁-C₈-alkyl.

-   W especially represents methoxy, ethoxy, n-propoxy, iso-propoxy,    n-butoxy, iso-butoxy, sec-butoxy, methoxy-ethyloxy, ethoxy-ethyloxy    or cyclopropylmethoxy,

-   X especially represents methyl or ethyl,

-   Y especially represents chlorine,

-   CKE especially represents one of the groups

-   A especially represents hydrogen, methyl, ethyl, cyclopropyl,    isopropyl, n-propyl, isobutyl, n-butyl, t-butyl or s-butyl (in    particular hydrogen, methyl or ethyl),-   B especially represents hydrogen, methyl or ethyl,-   A, B and the carbon atom to which they are bonded especially    represent saturated C₅-C₆-cycloalkyl in which one ring member is    optionally replaced by oxygen and which is optionally    monosubstituted by methyl, methoxy, ethoxy, n-propoxy, n-butoxy or    trifluoromethyl (in particular methyl or methoxy),-   D especially represents hydrogen, methyl, ethyl, isopropyl,    cyclopropyl or cyclohexyl,    or-   A and D together especially represent C₃-C₅-alkanediyl or the group    AD-1,-   G especially represents hydrogen (a) or one of the groups

—SO₂—R³ (d) or E (f)

-   -   in which    -   L represents oxygen,    -   M represents oxygen and    -   E represents an ammonium ion (N⁺(C₆H₁₃)₄),

-   R¹ especially represents C₁-C₈-alkyl; C₁-C₂-alkoxy-C₁-alkyl, or    C₂-C₁₇-alkenyl,

-   R² especially represents C₁-C₈-alkyl or C₂-C₆-alkenyl,

-   R³ especially represents C₁-C₄-alkyl.

The abovementioned definitions of radicals or illustrations, in generalor where preferred ranges have been mentioned, can be combined with eachother as desired, that is to say combinations between the respectiveranges and preferred ranges are also possible. They apply to the endproducts and, analogously, to the precursors and intermediates.

Preferred according to the invention are the compounds of the formula(I) which contain a combination of the meanings mentioned above as beingpreferred (preferable).

Particularly preferred according to the invention are the compounds ofthe formula (I) which contain a combination of the meanings mentionedabove as being especially preferred.

Very particularly preferred according to the invention are the compoundsof the formula (I) which contain a combination of the meanings mentionedabove as being very especially preferred.

The compounds of the formula (I) with a combination of the meaningsmentioned above preceded by “especially” are especially preferred inaccordance with the invention.

Saturated or unsaturated hydrocarbon radicals, such as alkyl, alkanediylor alkenyl, also in connection with hetero atoms, such as, for example,in alkoxy, can be in each case straight-chain or branched as far as thisis possible.

Unless stated otherwise, optionally substituted radicals can bemonosubstituted or polysubstituted, it being possible for thesubstituents to be identical or different in the case of thepolysubstituted radicals.

Compounds of the formula (I-1-a) which may be mentioned individually inaddition to the compounds mentioned in the preparation examples arethose which follow:

TABLE 1

A B D CH₃ H H C₂H₅ H H C₃H₇ H H i-C₃H₇ H H C₄H₉ H H i-C₄H₉ H H s-C₄H₉ HH t-C₄H₉ H H CH₃ CH₃ H C₂H₅ CH₃ H C₃H₇ CH₃ H i-C₃H₇ CH₃ H C₄H₉ CH₃ Hi-C₄H₉ CH₃ H s-C₄H₉ CH₃ H t-C₄H₉ CH₃ H C₂H₅ C₂H₅ H C₃H₇ C₃H₇ H

CH₃ H

CH₃ H

CH₃ H —(CH₂)₂— H —(CH₂)₄— H —(CH₂)₅— H —(CH₂)₆— H —(CH₂)₇— H—(CH₂)₂—O—(CH₂)₂— H —CH₂—O—(CH₂)₃— H —(CH₂)₂—S—(CH₂)₂— H—CH₂—CHCH₃—(CH₂)₃— H —(CH₂)₂—CHCH₃—(CH₂)₂— H —(CH₂)₂—CHC₂H₅—(CH₂)₂— H—(CH₂)₂—CHC₃H₇—(CH₂)₂— H —(CH₂)₂—CHi-C₃H₇—(CH₂)₂— H—(CH₂)₂—CHOCH₃—(CH₂)₂— H —(CH₂)₂—CHOC₂H₅—(CH₂)₂— H—(CH₂)₂—CHOC₃H₇—(CH₂)₂— H —(CH₂)₂—CHO—i-C₃H₇—(CH₂)₂— H—(CH₂)₂—C(CH₃)₂—(CH₂)₂— H —CH₂—(CHCH₃)₂—(CH₂)₂— H

H

H

H

H

H A D B —(CH₂)₃— H —(CH₂)₄— H —CH₂—CHCH₃—CH₂— H —CH₂—CH₂—CHCH₃— H—CH₂—CHCH₃—CHCH₃— H —CH₂—CH(OCH₃)—CH₂— H —CH₂—CH═CH—CH₂— H

H —CH₂—S—CH₂— H —CH₂—S—(CH₂)₂— H —(CH₂)₂—S—CH₂— H

H H CH₃ H H C₂H₅ H H C₃H₇ H H i-C₃H₇ H H

H H

H H

H CH₃ CH₃ H CH₃ C₂H₅ H CH₃ C₃H₇ H CH₃ i-C₃H₇ H CH₃

H CH₃

H CH₃

H

H C₂H₅ CH₃ H C₂H₅ C₂H₅ H W = OCH₃, X = CH₃ Y = Cl.

TABLE 2 A, B and D as shown in Table 1 W = OCH₃; X = CH₃; Y = Br

TABLE 3 A, B and D as shown in Table 1 W = OCH₃; X = C₂H₅; Y = Cl.

TABLE 4 A, B and D as shown in Table 1 W = OCH₃; X = C₂H₅; Y = Br.

TABLE 5 A, B and D as shown in Table 1 W = OC₂H₅; X = CH₃; Y = Cl.

TABLE 6 A, B and D as shown in Table 1 W = OC₂H₅; X = C₂H₅; Y = Cl.

Compounds of the formula (I-2-a) which may be mentioned individually inaddition to the compounds mentioned in the preparation examples arethose which follow:

TABLE 7

A B CH₃ H C₂H₅ H C₃H₇ H i-C₃H₇ H C₄H₉ H i-C₄H₉ H s-C₄H₉ H t-C₄H₉ H CH₃CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉ CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇— —(CH₂)₂—O—(CH₂)₂——CH₂—O—(CH₂)₃— —(CH₂)₂—S —(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃——(CH₂)₂—CHCH₃—(CH₂)₂— (CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂——(CH₂)₂—CHi-C₃H₇—(CH₂)₂— —(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂——(CH₂)₂—CHOC₃H₇—(CH₂)₂— —(CH₂)₂—CHO—i-C₃H₇—(CH₂)₂——(CH₂)₂—C(CH₃)₂—(CH₂)₂— —CH₂—(CHCH₃)₂—(CH₂)₂—

W = OCH₃, X = CH₃, Y = Cl.

TABLE 8 A and B as shown in Table 7 W = OCH₃; X = CH₃;Y = Br.

TABLE 9 A and B as shown in Table 7 W = OCH₃; X = C₂H₅; Y = Cl.

TABLE 10 A and B as shown in Table 7 W = OCH₃; X = C₂H₅; Y = Br.

TABLE 11 A and B as shown in Table 7 W = OC₂H₅; X = CH₃; Y = Cl.

TABLE 12 A and B as shown in Table 7 W = OC₂H₅; X = C₂H₅; Y = Cl.

The following compounds of the formula (I-8-a) may be mentionedindividually in addition to compounds mentioned in the preparationexamples:

TABLE 13

A D CH₃ CH₃ CH₃ —(CH₂)₂OH— CH₃ —(CH₂)₂OCH₃— CH₃ —(CH₂)₂—O—(CH₂)₂—OCH₃——(CH₂)₂—O—CH₃— —(CH₂)₂—O—CH₃— —(CH₂)₂—O—(CH₂)₂—OCH₃——(CH₂)₂—O—(CH₂)₂—OCH₃— —(CH₂)₃— —(CH₂)₄— —(CH2)₂—O—(CH₂)₂—

W = OCH₃, X = CH₃, Y = Cl.

TABLE 14 A and D as shown in Table 13 W = OCH₃; X = CH₃; Y = Br.

TABLE 15 A and D as shown in Table 13 W = OCH₃; X = C₂H₅; Y = Cl.

TABLE 16 A and D as shown in Table 13 W = OCH₃; X = C₂H₅; Y = Br.

TABLE 17 A and D as shown in Table 13 W = OC₂H₅; X = CH₃; Y = Cl.

TABLE 18 A and D as shown in Table 13 W = OC₂H₅; X = C₂H₅; Y = Cl.

Preferred meanings of the groups mentioned above in connection with thecompounds improving crop plant tolerance (“herbicide safeners”) of theformulae (IIa), (IIb), (IIe), (IId) and (IIe) are defined hereinbelow.

-   n preferably represents the numbers 0, 1, 2, 3 or 4.-   A¹ preferably represents one of the divalent heterocyclic groups    outlined hereinbelow

-   A² preferably represents methylene or ethylene, each of which is    optionally substituted by methyl, ethyl, methoxycarbonyl or    ethoxycarbonyl.-   R¹⁴ preferably represents hydroxyl, mercapto, amino, methoxy,    ethoxy, n- or i-propoxy, n-, s- or t-butoxy, methylthio, ethylthio,    n- or i-propylthio, n-, s- or t-butylthio, methylamino, ethylamino,    n-oder i-propylamino, n-, s- or t-butylamino, dimethylamino or    diethylamino.-   R¹⁵ preferably represents hydroxyl, mercapto, amino, methoxy,    ethoxy, n- or i-propoxy, n-, s- or t-butoxy, methylthio, ethylthio,    n- or i-propylthio, n-, s- or t-butylthio, methylamino, ethylamino,    n- or i-propylamino, n-, s- or t-butyl-amino, dimethylamino or    diethylamino.-   R¹⁶ preferably represents methyl, ethyl, n- or i-propyl, each of    which is optionally substituted by fluorine, chlorine and/or    bromine.-   R¹⁷ preferably represents hydrogen, or represents methyl, ethyl, n-    or i-propyl, n-, s- or t-butyl, propenyl, butenyl, propinyl or    butinyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl,    dioxolanylmethyl, furyl, furylmethyl, thienyl, thiazolyl,    piperidinyl, each of which is optionally substituted by fluorine    and/or chlorine, or represents phenyl which is optionally    substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl,    n-, s- or t-butyl.-   R¹⁸ preferably represents hydrogen, or represents methyl, ethyl, n-    or i-propyl, n-, s- or t-butyl, propenyl, butenyl, propinyl or    butinyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl,    dioxolanylmethyl, furyl, furylmethyl, thienyl, thiazolyl,    piperidinyl, each of which is optionally substituted by fluorine    and/or chlorine, or represents phenyl which is optionally    substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl,    n-, s- or t-butyl or together with R¹⁷ represents one of the    radicals —CH₂—O—CH₂—CH₂— and —CH₂—CH₂—O—CH₂—CH₂— which are    optionally substituted by methyl, ethyl, furyl, phenyl, a fused    benzene ring or by two substituents which, together with the carbon    atom to which they are bonded, form a 5- or 6-membered carbocycle.-   R¹⁹ preferably represents hydrogen, cyano, fluorine, chlorine,    bromine, or represents methyl, ethyl, n- or i-propyl, cyclopropyl,    cyclobutyl, cyclopentyl, cyclohexyl or phenyl, each of which is    optionally substituted by fluorine, chlorine and/or bromine.-   R²⁰ preferably represents hydrogen, or represents methyl, ethyl, n-    or i-propyl, n-, s- or t-butyl, in each case optionally substituted    by hydroxyl, cyano, fluorine, chlorine, methoxy, ethoxy, n- or    i-propoxy.-   R²⁰ preferably represents hydrogen, cyano, fluorine, chlorine,    bromine, or represents methyl, ethyl, n- or i-propyl, n-, s- or    t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl,    each of which is optionally substituted by fluorine, chlorine and/or    bromine.-   X¹ preferably represents nitro, cyano, fluorine, chlorine, bromine,    methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, difluoromethyl,    dichloromethyl, trifluoromethyl, trichloromethyl,    chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or    i-propoxy, difluoromethoxy or trifluoromethoxy.-   X² preferably represents hydrogen, nitro, cyano, fluorine, chlorine,    bromine, methyl, ethyl, n- or i-propyl, n-, s- or t-butyl,    difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl,    chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or    i-propoxy, difluoromethoxy or trifluoromethoxy.-   X³ preferably represents hydrogen, nitro, cyano, fluorine, chlorine,    bromine, methyl, ethyl, n- or i-propyl, n-, s- or t-butyl,    difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl,    chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or    i-propoxy, difluoromethoxy or trifluoromethoxy.-   R²² preferably represents hydrogen, methyl, ethyl, n- or i-propyl.-   R²³ preferably represents hydrogen, methyl, ethyl, n- or i-propyl.-   R²⁴ preferably represents hydrogen, or represents methyl, ethyl, n-    or i-propyl, n-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,    n-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-,    s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-,    s- or t-butylamino, dimethylamino or diethylamino, each of which is    optionally substituted by cyano, fluorine, chlorine, methoxy,    ethoxy, n- or i-propoxy, or represents cyclopropyl, cyclobutyl,    cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy,    cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio,    cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutyl-amino,    cyclopentylamino or cyclohexylamino, each of which is optionally    substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n-    or i-propyl.-   R²⁵ preferably represents hydrogen, or represents methyl, ethyl, n-    or i-propyl, n-, i- or s-butyl, each of which is optionally    substituted by cyano, hydroxyl, fluorine, chlorine, methoxy, ethoxy,    n- or i-propoxy, or represents propenyl, butenyl, propinyl or    butinyl, each of which is optionally substituted by cyano, fluorine,    chlorine or bromine, or represents cyclopropyl, cyclobutyl,    cyclopentyl or cyclohexyl, each of which is optionally substituted    by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or    i-propyl.-   R²⁶ preferably represents hydrogen, or represents methyl, ethyl, n-    or i-propyl, n-, i- or s-butyl, each of which is optionally    substituted by cyano, hydroxyl, fluorine, chlorine, methoxy, ethoxy,    n- or i-propoxy, or represents propenyl, butenyl, propinyl or    butinyl, each of which is optionally substituted by cyano, fluorine,    chlorine or bromine, or represents cyclopropyl, cyclobutyl,    cyclopentyl or cyclohexyl, each of which is optionally substituted    by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or    i-propyl, or represents phenyl which is optionally substituted by    nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or    i-propyl, n-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or    i-propoxy, difluoromethoxy or trifluoromethoxy, or together with R²⁵    represents butane-1,4-diyl(trimethylene), pentane-1,5-diyl,    1-oxabutane-1,4-diyl or 3-oxapentane-1,5-diyl, each of which is    optionally substituted by methyl or ethyl.-   X⁴ preferably represents nitro, cyano, carboxyl, carbamoyl, formyl,    sulphamoyl, hydroxyl, amino, fluorine, chlorine, bromine, methyl,    ethyl, n- or i-propyl, n-, s- or t-butyl, trifluoromethyl, methoxy,    ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.-   X⁵ preferably represents nitro, cyano, carboxyl, carbamoyl, formyl,    sulphamoyl, hydroxyl, amino, fluorine, chlorine, bromine, methyl,    ethyl, n- or i-propyl, n-, s- or t-butyl, trifluoromethyl, methoxy,    ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.

Examples of the compounds of the formula (IIa) which are very especiallypreferred as herbicide safeners according to the invention are listed inthe table which follows.

TABLE Examples of the compounds of the formula (IIa) (IIa)

Example (Positions) No. (X¹)_(n) A¹ R¹⁴ IIa-I (2) Cl, (4) Cl

OCH₃ IIa-2 (2) Cl, (4) Cl

OCH₃ IIa-3 (2) Cl, (4) Cl

OC₂H₅ IIa-4 (2) Cl, (4) Cl

OC₂H₅ IIa-5 (2) Cl

OCH₃ IIa-6 (2) Cl, (4) Cl

OCH₃ IIa-7 (2) F

OCH₃ IIa-8 (2) F

OCH₃ IIa-9 (2) Cl, (4) Cl

OC₂H₅ IIa-10 (2) Cl, (4) CF₃

OCH₃ IIa-11 (2) Cl

OCH₃ IIa-12 —

OC₂H₅ IIa-13 (2) Cl, (4) Cl

OC₂H₅ IIa-14 (2) Cl, (4) Cl

OC₂H₅ IIa-15 (2) Cl, (4) Cl

OC₂H₅ IIa-16 (2) Cl, (4) Cl

OC₂H₅ IIa-17 (2) Cl, (4) Cl

OC₂H₅ IIa-18 —

OH

Examples of the compounds of the formula (IIb) which are very especiallypreferred as herbicide safeners according to the invention are listed inthe table which follows.

TABLE Examples of the compounds of the formula (IIb) Ex- am- (Posi-(Posi- ple tion) tion) No. X² X³ A¹ R¹⁵ IIb-1 (5) — CH₂ OH Cl IIb-2 (5)— CH₂ OCH₃ Cl IIb-3 (5) — CH₂ OC₂H₅ Cl IIb-4 (5) — CH₂ OC₃H₇-n Cl IIb-5(5) — CH₂ OC₃H₇-i Cl IIb-6 (5) — CH₂ OC₄H₉-n Cl IIb-7 (5) — CH₂OCH(CH₃)C₅H₁₁-n Cl IIb-8 (5) (2) CH₂ OH Cl F IIb-9 (5) (2) CH₂ OH Cl ClIIb-10 (5) — CH₂ OCH₂CH═CH₂ Cl IIb-11 (5) — CH₂ OC₄H₉-i Cl IIb-12 (5) Cl— CH₂

IIb-13 (5) Cl —

OCH₂CH═CH₂ IIb-14 (5) Cl —

OC₂H₅ IIb-15 (5) Cl —

OCH₃

Examples of the compounds of the formula (IIc) which are very especiallypreferred as herbicide safeners according to the invention are listed inthe table which follows.

TABLE Examples of the compounds of the formula (IIc) (IIc)

Example No. R¹⁶ N(R¹⁷,R¹⁸) IIc-1 CHCl₂ N(CH₂CH═CH₂)₂ IIc-2 CHCl₂

IIc-3 CHCl₂

IIc-4 CHCl₂

IIc-5 CHCl₂

IIc-6 CHCl₂

IIc-7 CHCl₂

Examples of the compounds of the formula (IId) which are very especiallypreferred as herbicide safeners according to the invention are listed inthe table which follows.

TABLE Examples of the compounds of the formula (IId) (IId)

Example (Positions) (Positions) No. R²² R²³ R²⁴ (X⁴)_(n) (X⁵)_(n) IId-1H H CH₃ (2) OCH₃ — IId-2 H H C₂H₅ (2) OCH₃ — IId-3 H H C₃H₇-n (2) OCH₃ —IId-4 H H C₃H₇-i (2) OCH₃ — IId-5 H H

(2) OCH₃ — IId-6 H H CH₃ (2) OCH₃ — (5) CH₃ IId-7 H H C₂H₅ (2) OCH₃ —(5) CH₃ IId-8 H H C₃H₇-n (2) OCH₃ — (5) CH₃ IId-9 H H C₃H₇-i (2) OCH₃ —(5) CH₃ IId-10 H H

(2) OCH₃ (5) CH₃ — IId-11 H H OCH₃ (2) OCH₃ — (5) CH₃ IId-12 H H OC₂H₅(2) OCH₃ — (5) CH₃ IId-13 H H OC₃H₇-i (2) OCH₃ — (5) CH₃ IId-14 H H SCH₃(2) OCH₃ — (5) CH₃ I1d-15 H H SC₂H₅ (2) OCH₃ — (5) CH₃ IId-16 H HSC₃H₇-i (2) OCH₃ — (5) CH₃ IId-17 H H NHCH₃ (2) OCH₃ — (5) CH₃ IId-18 HH NHC₂H₅ (2) OCH₃ — (5) CH₃ IId-19 H H NHC₃H₇-i (2) OCH₃ — (5) CH₃IId-20 H H

(2) OCH₃ (5) CH₃ — IId-21 H H NHCH₃ (2) OCH₃ — IId-22 H H NHC₃H₇-i (2)OCH₃ — IId-23 H H N(CH₃)₂ (2) OCH₃ — IId-24 H H N(CH₃)₂ (3) CH₃ — (4)CH₃ IId-25 H H CH₂—O—CH₃ (2) OCH₃ —

Examples of the compounds of the formula (IIe) which are very especiallypreferred as herbicide safeners according to the invention are listed inthe table which follows.

TABLE Examples of the compounds of the formula (IIe) (IIe)

Example (Positions) (Positions) No. R²² R²⁵ R²⁶ (X⁴)_(n) (X⁵)_(n) IIe-1H H CH₃ (2) OCH₃ — IIe-2 H H C₂H₅ (2) OCH₃ — IIe-3 H H C₃H₇-n (2) OCH₃ —IIe-4 H H C₃H₇-i (2) OCH₃ — IIe-5 H H

(2) OCH₃ — IIe-6 H CH₃ CH₃ (2) OCH₃ — IIe-7 H H CH₃ (2) OCH₃ — (5) CH₃IIe-8 H H C₂H₅ (2) OCH₃ — (5) CH₃ IIe-9 H H C₃H₇-n (2) OCH₃ — (5) CH₃IIe-10 H H C₃H₇-i (2) OCH₃ — (5) CH₃ IIe-11 H H

(2) OCH₃ (5) CH₃ — IIe-12 H CH₃ CH₃ (2) OCH₃ — (5) CH₃

Cloquintocet-mexyl, fenchlorazol-ethyl, isoxadifen-ethyl,mefenpyr-diethyl, furilazole, fenclorim, cumyluron, dymron, dimepiperateand the compounds IIe-5 and IIe-11 are most preferred as the compoundwhich improves crop plant tolerance [component (b′)], withcloquintocet-mexyl and mefenpyr-diethyl being especially preferred.

The compounds of the general formula (IIa) to be used in accordance withthe invention as safeners are known and/or can be prepared by methodsknown per se (cf. WO-A-91/07874, WO-A-95/07897).

The compounds of the general formula (IIb) to be used in accordance withthe invention as safeners are known and/or can be prepared by methodsknown per se (cf. EP-A-191736).

The compounds of the general formula (IIe) to be used in accordance withthe invention as safeners are known and/or can be prepared by methodsknown per se (cf. DE-A-2218097, DE-A-2350547).

The compounds of the general formula (IId) to be used in accordance withthe invention as safeners are known and/or can be prepared by methodsknown per se (cf. DE-A-19621522/U.S. Pat. No. 6,235,680).

The compounds of the general formula (IIe) to be used in accordance withthe invention as safeners are known and/or can be prepared by methodsknown per se (cf WO-A-99/66795/U.S. Pat. No. 6,251,827).

Examples of the selectively herbicidal combinations according to theinvention of in each case one active compound of the formula (I) and ineach case one of the above-defined safeners are listed in the tablewhich follows.

TABLE Examples of the combinations according to the invention Activecompounds of the formula (I) Safener I-1 cloquintocet-mexyl I-1fenchlorazole-ethyl I-1 isoxadifen-ethyl I-1 mefenpyr-diethyl I-1furilazole I-1 fenclorim I-1 cumyluron I-1 daimuron/dymron I-1dimepiperate I-1 Ile-11 I-1 Ile-5 I-2 cloquintocet-mexyl I-2fenchlorazole-ethyl I-2 isoxadifen-ethyl I-2 mefenpyr-diethyl I-2furilazole I-2 fenclorim I-2 cumyluron I-2 daimuron/dymron I-2dimepiperate I-2 Ile-11 I-2 Ile-5 I-3 cloquintocet-mexyl I-3fenchlorazole-ethyl I-3 isoxadifen-ethyl I-3 mefenpyr-diethyl I-3furilazole I-3 fenclorim I-3 cumyluron I-3 daimuron/dymron I-3dimepiperate I-3 Ile-5 I-3 Ile-11 I-4 cloquintocet-mexyl I-4fenchlorazole-ethyl I-4 isoxadifen-ethyl I-4 mefenpyr-diethyl I-4furilazole I-4 fenclorim I-4 cumyluron I-4 daimuron/dymron I-4dimepiperate I-4 Ile-11 I-4 Ile-5 I-5 cloquintocet-mexyl I-5fenchlorazole-ethyl I-5 isoxadifen-ethyl I-5 mefenpyr-diethyl I-5furilazole I-5 fenclorim I-5 cumyluron I-5 daimuron/dymron I-5dimepiperate I-5 Ile-5 I-5 Ile-11 I-6 cloquintocet-mexyl I-6fenchlorazole-ethyl I-6 isoxadifen-ethyl I-6 mefenpyr-diethyl I-6furilazole I-6 fenclorim I-6 cumyluron I-6 daimuron/dymron I-6dimepiperate I-6 Ile-5 I-6 Ile-11 I-7 cloquintocet-mexyl I-7fenchlorazole-ethyl I-7 isoxadifen-ethyl I-7 mefenpyr-diethyl I-7furilazole I-7 fenclorim I-7 cumyluron I-7 daimuron/dymron I-7dimepiperate I-7 Ile-5 I-7 Ile-11 I-8 cloquintocet-mexyl I-8fenchlorazole-ethyl I-8 isoxadifen-ethyl I-8 mefenpyr-diethyl I-8furilazole I-8 fenclorim I-8 cumyluron I-8 daimuron/dymron I-8dimepiperate I-8 Ile-5 I-8 Ile-11

Surprisingly, it has now been found that the above-defined activecompound combinations of substituted cyclic ketoenols of the generalformula (I) and safeners (antidotes) from the above group (b′) are notonly very well tolerated by useful plants, but also have a particularlyhigh herbicidal activity and can be used in a variety of crops, inparticular in cereals (mainly wheat), but also in soybeans, potatoes,maize and rice, for the selective control of weeds.

It must be considered as surprising that, from a multiplicity of knownsafeners or antidotes which are capable of antagonizing the damagingeffect of a herbicide on the crop plants, it is precisely theabovementioned compounds of group (b′) which are capable of virtuallycompletely compensating for the harmful effect of substituted cyclicketoenols on the crop plants without adversely affecting the herbicidalactivity towards the weeds to a substantial degree.

What must be emphasized in this context is the particularly advantageousactivity of the particularly and most preferred components from group(b′), in particular with regard to leaving cereal plants, such as, forexample, wheat, barley and rye, but also maize and rice, as crop plantsunharmed.

If, for example, in accordance with process (A) ethylN-(2-methyl-4-chloro-6-methoxyphenylacetyl)-1-aminocyclohexanecarboxylateis used as starting material, the course of the process according to theinvention can be represented by the following equation:

If, for example, in accordance with process (B) ethylO-(2-ethyl-4-chloro-6-methoxyphenylacetyl)-2-hydroxyisobutyrate is used,the course of the process according to the invention can be representedby the following equation:

If, for example, in accordance with process (C) ethyl2-(2-methyl-4-chloro-6-methoxy-phenyl)-4-(4-methoxy)benzylmercapto-4-methyl-3-oxovalerateis used, the course of the process according to the invention can berepresented by the following equation:

If, for example, in accordance with process (D) chlorocarbonyl2-(2-ethyl-4-chloro-6-methoxy)phenyl) ketene and acetone are used asstarting compounds, the course of the process according to the inventioncan be represented by the following equation:

If, for example, in accordance with process (E) chlorocarbonyl2-(2-ethyl-4-chloro-6-methoxy)phenyl) ketene and thiobenzamide are usedas starting compounds, the course of the process according to theinvention can be represented by the following equation:

If, for example, in accordance with process (F) ethyl5-(2-ethyl-4-chloro-6-methoxyphenyl)-2,3-trimethylene-4-oxovalerate isused, the course of the process according to the invention can berepresented by the following equation:

If, for example, in accordance with process (G) ethyl5-[(2-ethyl-4-chloro-6-methoxy)-phenyl]-2-methyl-5-oxo-hexanoate is usedas starting material, the course of the process according to theinvention can be represented by the following equation:

If, for example, in accordance with process (Hα) hexahydropyridazine andchlorocarbonyl 2-(2-ethyl-4-chloro-6-methoxy)phenyl ketene are used asstarting compounds, the course of the process according to the inventioncan be represented by the following equation:

If, for example, in accordance with process (H) hexahydropyridazine anddimethyl (2-ethyl-4-chloro-6-methoxy)phenylmalonate are used as startingmaterials, the course of the process according to the invention can berepresented by the following equation:

If, for example, in accordance with process (Hγ)1-ethoxycarbonyl-2-[(2-methyl-4-bromo-6-methoxy)phenylacetyl]hexahydropyridazineis used as starting material, the course of the reaction can berepresented by the following equation:

If, for example, in accordance with process (Iα)3-(2-methyl-4-chloro-6-methoxyphenyl)-5,5-dimethylpyrrolidine-2,4-dioneand pivaloyl chloride are used as starting materials, the course of theprocess according to the invention can be represented by the followingequation:

If, for example, in accordance with process (Iβ)3-(2-ethyl-4-chloro-6-methoxyphenyl)-4-hydroxy-5-phenyl-Δ³-dihydrofuran-2-oneand acetic anhydride are used as starting materials, the course of theprocess according to the invention can be represented by the followingequation:

If, for example, in accordance with process (J)8-[(2-ethyl-4-chloro-6-methoxy)phenyl]-1-azabicyclo-[4.3.0^(1,6)]-nonane-7,9-dioneand ethoxyethyl chloroformate are used as starting materials, the courseof the process according to the invention can be represented by thefollowing equation:

If, for example, in accordance with process (K),3-(2-ethyl-4-chloro-6-methoxyphenyl)-4-hydroxy-5-methyl-6-(3-pyridyl)pyroneand methyl chloromonothioformate are used as starting materials, thecourse of the reaction can be represented by the following equation:

If, for example, in accordance with process (L)3-(2-methyl-4-chloro-6-methoxyphenyl)-5,5-pentamethylenepyrrolidine-2,4-dioneand methanesulphonyl chloride are used as starting materials, the courseof the reaction can be represented by the following equation:

If, for example, in accordance with process (M)3-(2-ethyl-4-chloro-6-methoxyphenyl)-4-hydroxy-5,5-dimethyl-Δ³-dihydrofuran-2-oneand 2,2,2-trifluoroethyl methanechlorothiophosphonate are used asstarting materials, the course of the reaction can be represented by thefollowing equation:

If, for example, in accordance with process (N),3-(2-ethyl-4-chloro-6-methoxyphenyl)-5-cyclopropyl-5-methylpyrrolidine-2,4-dioneand NaOH are used as components, the course of the process according tothe invention can be represented by the following equation:

If, for example, in accordance with process (O), variant α,3-(2-ethyl-4-chloro-6-methoxyphenyl)-4-hydroxy-5-tetramethylene-Δ³-dihydrofuran-2-oneand ethyl isocyanate are used as starting materials, the course of thereaction can be represented by the following equation:

If, for example, in accordance with process (O), variant β,3-(2-methyl-4-chloro-6-methoxyphenyl)-5-methylpyrrolidine-2,4-dione anddimethylcarbamoyl chloride are used as starting materials, the course ofthe reaction can be represented by the following equation:

If, for example, in accordance with process (P),3-(2-bromo-4-chloro-6-ethylphenyl)-5,5-dimethylpyrrolidine-2,4-dione andsodium methoxide are used as starting materials, the course of thereaction can be represented by the following scheme:

The compounds of the formula (II)

in which

-   A, B, D, W, X, Y and R⁸ have the abovementioned meanings    and which are required as starting materials in process (a)    according to the invention are new.

The acylamino acid esters of the formula (II) are obtained, for example,when amino acid derivatives of the formula (XXIII)

in which

-   A, B, R⁸ and D have the abovementioned meanings    are acylated with substituted phenylacetic acid derivatives of the    formula (XXIV)

in which

-   W, X and Y have the abovementioned meanings and-   Z represents a leaving group introduced by reagents for the    activation of carboxylic acids, such as carbonyldiimidazole,    carbonyldiimides (such as, for example, dicyclohexylcarbodiimide),    phosphorylating reagents (such as, for example, POCl₃, BOP-Cl),    halogenating agents, for example thionyl chloride, oxalyl chloride,    phosgene or chloroformic esters,    (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem. 6    341-5, 1968)    or when acylamino acids of the formula (XXV)

in which

-   A, B, D, W, X and Y have the abovementioned meanings    are esterified (Chem. Ind. (London) 1568 (1968)).

The compounds of the formula (XXV)

in which

-   A, B, D, W, X and Y have the abovementioned meanings    are new.

The compounds of the formula (XXV) are obtained when amino acids of theformula (XXVI)

in which

-   A, B and D have the abovementioned meanings    are acylated with substituted phenylacetic acid derivatives of the    formula (XXIV)

in which

-   W, X and Y have the abovementioned meanings and-   Z has the abovementioned meaning    for example in a Schotten-Baumann reaction (Organikum [Laboratory    Practical in Organic Chemistry], VEB Deutscher Verlag der    Wissenschaften, Berlin 1977, p. 505).

The compounds of the formula (XXIV) are new. They can be prepared byprocesses known in principle and as can be seen from the examples (see,for example, H. Henecka, Houben-Weyl, Methoden der Organischen Chemie[Methods in Organic Chemistry], Vol. 8, pp. 467-469 (1952)).

The compounds of the formula (XXIV) are obtained, for example, byreacting substituted phenylacetic acids of the formula (XXVII)

in which

-   W, X and Y have the abovementioned meanings    with halogenating agents (for example thionyl chloride, thionyl    bromide, oxalyl chloride, phosgene, phosphorus trichloride,    phosphorus tribromide or phosphorus pentachloride), phosphonylating    reagents (such as, for example, POCl₃, BOP—Cl), carbonyldiimidazole,    carbonyldiimides (for example dicyclohexylcarbodiimide), if    appropriate in the presence of a diluent (for example optionally    chlorinated aliphatic or aromatic hydrocarbons such as toluene or    methylene chloride or ethers, for example tetrahydrofuran, dioxane,    methyl tert-butyl ether) at temperatures of from −20° C. to 150° C.,    preferably from −10° C. to 100° C.

Some of the compounds of the formulae (XXIII) and (XXVI) are knownand/or can be synthesized by known processes (see, for example,Compagnon, Miocque Ann. Chim. (Paris) [14] 5 pp. 11-22, 23-27 (1970)).

The substituted cyclic amino carboxylic acids of the formula (XXVI) inwhich A and B form a ring are generally obtained by means of aBucherer-Bergs synthesis or a Strecker synthesis, where they areobtained in each case in various isomeric forms. Thus, the conditions ofthe Bucherer-Bergs synthesis preferentially give the isomers (forsimplicity's sake termed β hereinbelow) in which the radicals R and thecarboxyl group are in the equatorial position, while the conditions ofthe Strecker synthesis preferentially give the isomers (for simplicity'ssake termed hereinbelow) where the amino group and the radicals R are inthe equatorial position.

(L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C. Jitrangeri, Can.J. Chem. 53 3339 (1975).

Furthermore, the starting substances of the formula (II)

where

-   A, B, D, W, X, Y and R⁸ have the abovementioned meanings    and which are used in the above process (A)    can be prepared when amino nitriles of the formula (XXVIII)

in which

-   A, B and D have the abovementioned meanings    are reacted with substituted phenylacetic acid derivatives of the    formula (XXIV)

in which

-   W, X, Y and Z have the abovementioned meanings    to give compounds of the formula (XXIX)

in which

-   A, B, D, W, X and Y have the abovementioned meanings    and these are subsequently subjected to alcoholysis under acidic    conditions.

The compounds of the formula (XXIX) are also new.

The compounds of the formula (III)

in which

-   A, B, W, X, Y and R⁸ have the abovementioned meanings    and which are required as starting substances in process (B)    according to the invention are new.

They can be prepared by methods known in principle.

Thus, the compounds of the formula (III) are obtained, for example, when2-hydroxy carboxylic esters of the formula (XXX-A)

in which

-   A, B and R⁸ have the abovementioned meanings    are acylated with substituted phenylacetic acid derivatives of the    formula (XXIV)

in which

-   W, X and Y have the abovementioned meanings    (Chem. Reviews 52, 237-416 (1953)).

Furthermore, compounds of the formula (III) are obtained whensubstituted phenylacetic acids of the formula (XXVII)

in which

-   W, X and Y have the abovementioned meanings    are alkylated with -halogeno carboxylic esters of the formula    (XXX-B)

in which

-   A, B and R⁸ have the abovementioned meanings and-   Hal represents chlorine or bromine.

The compounds of the formula (XXVII) are new.

The compounds of the formula (XXX-B) are commercially available.

For example, the compounds of the formula (XXVII)

in which

-   W, X and Y have the abovementioned meanings,    are obtained when phenylacetic esters of the formula MOM

in which

-   W, X, Y and R⁸ have the abovementioned meanings    are hydrolysed under generally known standard conditions in the    presence of acids or bases, in the presence of a solvent.    Furthermore, phenylacetic acids of the formula (XXVII) are obtained    in accordance with process (Q).

The compounds of the formula (XXXI) are new.

The compounds of the formula (XXXI)

in which

-   W, X, Y and R⁸ have the abovementioned meanings    are obtained for example by process (R), which is described in the    examples, when phenylacetic esters of the formula (XXXI-a)

in which

-   R⁸, X and Y have the abovementioned meanings and-   W represents halogen (in particular bromine)    are reacted in the presence of an alcohol, in the presence of a base    and if appropriate in the presence of a catalyst (preferably copper    salts such as, for example, copper(1) bromide).

The phenylacetic esters of the formula (XXXI-a) are known in principlefrom the application. WO 96/35 664 and DE-A-10 301 804 and can beprepared by the methods described therein.

Moreover, phenylacetic esters of the formula (XXXI) are obtained byprocess (Q), which is described further below, by esterifying, bystandard methods, the phenylacetic acids of the formula (XXVII) obtainedin this process.

The compounds of the formula (IV)

in which

-   A, B, V, W, X, Y and R⁸ have the abovementioned meanings    and which are required as starting substances in the above    process (C) are new.

They can be prepared by methods known in principle.

The compounds of the formula (IV) are obtained, for example, whensubstituted phenylacetic esters of the formula (XXXI)

in which

-   W, X, Y and R⁸ have the abovementioned meanings    are acylated with 2-benzylthio-carboxylic halides of the formula    (XXXII)

in which

-   A, B and V have the abovementioned meanings and-   Hal represents halogen (in particular chlorine or bromine)    in the presence of strong bases (see, for example, M. S.    Chambers, E. J. Thomas, D. J. Williams, J. Chem. Soc. Chem. Commun.,    (1987), 1228).

Some of the benzylthio-carboxylic halides of the formula (XXXII) areknown and/or can be prepared by known processes (J. Antibiotics (1983),26, 1589).

The halogenocarbonyl ketenes of the formula (VI) which are required asstarting substances in the above processes (D), (E) and (H-α) are new.They can be prepared by methods known in principle (cf., for example,Org. Prep. Proced. Int. 7, (4), 155-158, 1975 and DE 1 945 703). Thus,for example, the compounds of the formula (VI)

in which

-   W, X and Y have the abovementioned meanings and-   Hal represents chlorine or bromine    are obtained when    substituted phenylmalonic acids of the formula (XXXIII)

in which

-   W, X and Y have the abovementioned meanings    are reacted with acid halides, such as, for example, thionyl    chloride, phosphorus(V) chloride, phosphorus(III) chloride, oxalyl    chloride, phosgene or thionyl bromide, if appropriate in the    presence of catalysts, such as, for example, dimethylformamide,    methyl-sterylformamide or triphenylphosphine, and, if appropriate,    in the presence of bases, such as, for example, pyridine or    triethylamine.

The substituted phenylmalonic acids of the formula (XXXIII) are new.They can be prepared in a simple manner by known processes (cf., forexample, Organikum [Laboratory Practical in Organic Chemistry], VEBDeutscher Verlag der Wissenschaften, Berlin 1977, p. 517 et seq.,EP-A-528 156, WO 96/35 664, WO 97/02 243, WO 97/01535, WO 97/36868 andWO 98/05638).

Thus, phenylmalonic acids of the formula (XXXIII)

in which

-   W, X and Y have the abovementioned meanings    are obtained when phenylmalonic esters of the formula (XI)

in which

-   W, X and Y have the abovementioned meanings-   and U represents OR⁸ or NH₂,    where R⁸ has the abovementioned meaning,    are initially hydrolysed in the presence of a base and a solvent and    subsequently acidified carefully (EP-A-528 156, WO 96/35 664, WO    97/02 243).

The malonic esters of the formula (XI)

in which

-   W, X and Y have the abovementioned meanings-   and U represents OR⁸ or NH₂,    where R⁸ has the abovementioned meaning,    are new.

They can be synthesized by generally known methods of organic chemistry(cf., for example, Tetrahedron Lett. 27, 2763 (1986), Organikum VEBDeutscher Verlag der Wissenschaften, Berlin 1977, p. 587 et seq., WO96/35664, WO 97/02243, WO 97/01535, WO 97/36868, WO 98/05638 and WO99/47525).

The carbonyl compounds of the formula (V)

in which

-   A and D have the abovementioned meanings    or their silyl enol ethers of the formula (Va)

in which

-   A, D and R⁸ have the abovementioned meanings    and which are required as starting substances for process (D)    according to the invention are compounds which are commercially    available, generally known or accessible by known processes.

The preparation of the ketene acid chlorides of the formula (VI) whichare required as starting substances for carrying out process (E)according to the invention have already been described above. Thethioamides of the formula (VII)

in which

-   A has the abovementioned meaning    and which are required for carrying out process (E) according to the    invention are compounds generally known in organic chemistry.

The compounds of the formula (VIII)

in which

-   A, B, Q¹, Q², W, X, Y and R⁸ have the abovementioned meanings    and which are required as starting materials in the above    process (F) are new.

They can be prepared by methods which are known in principle.

For example, the 5-aryl-4-ketocarboxylic esters of the formula (VIII)are obtained when 5-aryl-4-ketocarboxylic acids of the formula (XXXIV)

in which

-   W, X, Y, A, B, Q¹ and Q² have the abovementioned meanings    are esterified (cf., for example, Organikum, 15th edition, Berlin,    1977, page 499) or alkylated (see Preparation Example).-   The 5-aryl-4-ketocarboxylic acids of the formula (XXXIV)

in which

-   A, B, Q¹, Q², W, X and Y have the abovementioned meanings    are new, but can be prepared by methods which are known in principle    (WO 96/01 798, WO 97/14667, WO 98/39281).

For example, the 5-aryl-4-ketocarboxylic acids of the formula (XXXIV)are obtained when 2-phenyl-3-oxoadipic esters of the formula (XXXV)

in which

-   A, B, Q¹, Q², W, X and Y have the abovementioned meanings and-   R⁸ and R⁸′ represent alkyl (in particular C₁-C₈-alkyl) and,    when the compound of the formula (XXXVII-a) is employed, R⁸    represents hydrogen,    are decarboxylated, if appropriate in the presence of a diluent and    if appropriate in the presence of a base or acid (cf., for example,    Organikum, 15th edition, Berlin, 1977, pages 519 to 521).

The compounds of the formula (XXXV)

in which

-   A, B, Q¹, Q², W, Y, R⁸, R⁸′ have the abovementioned meanings and,    when the compound of the formula (XXXVII-a) is employed, R⁸    represents hydrogen re new.

The compounds of the formula (XXXV) are obtained, for example, whendicarboxylic semiester chlorides of the formula (XXXVI)

in which

-   A, B, Q¹, Q² and R⁸ have the abovementioned meanings and-   Hal represents chlorine or bromine    or carboxylic anhydrides of the formula (XXXVII-a)

in which

-   A, B, Q¹ and Q² have the abovementioned meanings are acylated with a    phenylacetic ester of the formula (XXXI)

in which

-   W, X, Y and R⁸′ have the abovementioned meanings in the presence of    a diluent and in the presence of a base (cf., for example, M. S.    Chambers, E. J. Thomas, D. J. Williams, J. Chem. Soc. Chem. Commun.,    (1987), 1228, cf. also the Preparation Examples).

Some of the compounds of the formulae (XXXVI) and (XXXVII-a) are knowncompounds of organic chemistry; alternatively, they can be prepared in asimple manner by methods which are known in principle.

The compounds of the formula (IX)

in which

-   A, B, Q³, Q⁴, Q⁵, Q⁶, W, X, Y and R⁸ have the abovementioned    meanings    and which are required as starting materials in the above    process (G) are new.

They can be prepared by methods which are known in principle.

For example, the 6-aryl-5-ketocarboxylic esters of the formula (IX) areobtained when 6-aryl-5-ketocarboxylic acids of the formula (XXXVIII)

in which

-   A, B, Q³, Q⁴, Q⁵, Q⁶, W, X and Y have the abovementioned meanings    are esterified (cf., for example, Organikum, 15th edition, Berlin,    1977, page 499).

The 6-aryl-5-ketocarboxylic acids of the formula (XXXVIII)

in which

-   A, B, Q³, Q⁴, Q⁵, Q⁶, W, X and Y have the abovementioned meanings    are new. They can be prepared by methods which are known in    principle (WO 99/43649, WO 99/48869), for example when substituted    2-phenyl-3-oxoheptanedioic esters of the formula (XXXIX)

in which

-   A, B, Q³, Q⁴, Q⁵, Q⁶, W, X and Y have the abovementioned meanings    and-   R⁸ and R⁸′ represent alkyl (preferably C₁-C₆-alkyl), and,    when the compound of the formula (XXXVII-b) is employed, R⁸    represents hydrogen, are hydrolysed and decarboxylated, if    appropriate in the presence of a diluent and if appropriate in the    presence of a base or acid (cf., for example, Organikum, 15th    edition, Berlin, 1977, pages 519 to 521).

The compounds of the formula (XXXIX)

in which

-   A, B, Q³, Q⁴, Q⁵, Q⁶, W, X, Y, R⁸ and R⁸′ have the abovementioned    meanings    are new and can be obtained    when dicarboxylic esters of the formula (XL)

in which

-   A, B, Q³, Q⁴, Q⁵, Q⁶ and R⁸ have the abovementioned meanings    or carboxylic anhydrides of the formula (XXXVII-b)

in which

-   A, B, Q³, (Q⁴, Q⁵, Q⁶ have the abovementioned meanings    are subjected to a condensation reaction with a substituted    phenylacetic ester of the formula (XXXI)

in which

-   W, X, Y and R⁸′ have the abovementioned meanings    in the presence of a diluent and in the presence of a base.

Some of the compounds of the formula (XL) are known; alternatively, theycan be synthesized by known processes.

Some of the hydrazines of the formula (X)

A-NH—NH-D  (X)

in which

-   A and D have the abovementioned meanings    and which are required as starting materials for processes (H-α) and    (H-β) according to the invention are known; alternatively, they can    be prepared by methods known from the literature (cf., for example,    Liebigs Ann. Chem. 585, 6 (1954); Reaktionen der organischen    Synthese [Reactions in organic synthesis], C. Ferri, pages 212, 513;    Georg Thieme Verlag Stuttgart, 1978; Liebigs Ann. Chem. 443 242    (1925); Chem. Ber. 98 2551 (1965), EP-A-508 126, WO 92/16510, WO    99/47 525, WO 01/17 972).

The compounds of the formula (XII)

in which

-   A, D, W, X, Y and R⁸ have the abovementioned meanings    and which are required for process (H-γ) according to the invention    are new.

The acylcarbazates of the formula (XII) are obtained for example whencarbazates of the formula (XLI)

in which

-   A, R⁸ and D have the abovementioned meanings    are acylated with substituted phenylacetic acid derivatives of the    formula (XXIV)

in which

-   W, X, Y and Z have the abovementioned meanings    (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem. 6,    341-5, 1968).

Some of the carbazates of the formula (XLI) are commercially availablecompounds, others are known compounds, or they can be prepared bymethods of organic chemistry which are known in principle.

The compounds of the formula (XXIV) have already been described incontext with the precursors for processes (A) and (B).

-   (Q) Moreover, phenylacetic acids of the formula (XXVII)

in which

-   W, X and Y have the abovementioned meanings    are obtained when phenylacetaldehydes of the formula (XLII)

in which

-   W, X and Y have the abovementioned meanings    are oxidized with suitable oxidants (such as, for example, NaOCl),    if appropriate in the presence of a solvent.

The compounds of the formula (XLII) are new.

Compounds of the formula (XLII)

in which

-   W, X and Y have the abovementioned meanings    are obtained when 3-phenylpropenes of the formula (XLIII)

in which

-   W, X and Y have the abovementioned meanings    are subjected to ozonolysis in the presence of a solvent and the    resulting ozonide is subjected to reductive work-up, for example    using dimethyl sulphide.

The 2-alkoxy-substituted 3-phenylpropenes of the formula (XVIII) whichare required for the preparation of the compounds of the formula (XLIII)are compounds of organic chemistry which are known in principle andwhich can be prepared by standard methods by alkylating phenols withallyl halides, followed by Claisen rearrangement and subsequentalkylation (WO 96/25 395).

The acid halides of the formula (XIII), carboxylic anhydrides of theformula (XIV), chloroformic esters or chloroformic thioesters of theformula (XV), chloromonothioformic esters or chlorodithioformic estersof the formula (XVI), sulphonyl chlorides of the formula (XVII),phosphorus compounds of the formula (XVIII), metal hydroxides, metalalkoxides or amines of the formulae (XIX) and (XX), isocyanates of theformula (XXI) and carbamoyl chlorides of the formula (XXII) which arefurthermore required as starting substances for carrying out processes(I), (J), (K), (L), (M), (N) and (O) according to the invention aregenerally known compounds of organic or inorganic chemistry.

The compounds of the formulae (V), (VII), (MIT) to (XXII), (XXIII),(XXVI), (XXVIII), (XXX-A), (XXX-B), (XXXII), (XXXVI), (XXXVII-a),(XXXVII-b), (XL) and (XLI) have furthermore been disclosed in the patentapplications cited at the outset and/or can be prepared by the methodsgiven therein.

Process (A) is characterized in that compounds of the formula (II) inwhich A, B, D, W, X, Y and R⁸ have the abovementioned meanings aresubjected to an intramolecular condensation in the presence of a base.

Diluents which can be employed in process (A) according to the inventionare all inert organic solvents. The following can preferably be used:hydrocarbons, such as toluene and xylene, furthermore ethers, such asdibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether anddiglycol dimethyl ether, furthermore polar solvents, such as dimethylsulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone, andalso alcohols, such as methanol, ethanol, propanol, isopropanol,butanol, iso-butanol and tert-butanol.

Bases (deprotonating agents) which can be employed when carrying outprocess (A) according to the invention are all customary protonacceptors. The following can preferably be used: oxides, hydroxides andcarbonates of alkali metals and alkaline earth metals, such as sodiumhydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodiumcarbonate, potassium carbonate and calcium carbonate, all of which canalso be employed in the presence of phase transfer catalysts, such as,for example, triethylbenzylammonium chloride, tetrabutylammoniumbromide, Adogen 464 (=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris-(methoxyethoxyethyl)-amine). Alkali metals, such as sodium orpotassium, can furthermore be used. Other substances which can beemployed are amides and hydrides of alkali metals and alkaline earthmetals, such as sodium amide, sodium hydride and calcium hydride, andfurthermore also alkali metal alcoholates, such as sodium methoxide,sodium ethoxide and potassium tert-butoxide.

When carrying out process (A) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (A) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (A) according to the invention, the reactantsof the formula (II) and the deprotonating bases are generally employedin approximately twice the equimolar amounts. However, it is alsopossible to use one or the other component in a larger excess (up to 3mol).

Process (B) is characterized in that compounds of the formula (III) inwhich A, B, W, X, Y and R⁸ have the abovementioned meanings aresubjected to an intramolecular condensation in the presence of a diluentand in the presence of a base.

Diluents which can be employed in process (B) according to the inventionare all inert organic solvents. The following can preferably be used:hydrocarbons, such as toluene and xylene, furthermore ethers, such asdibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether anddiglycol dimethyl ether, furthermore polar solvents, such as dimethylsulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone.Other substances which can be employed are alcohols, such as methanol,ethanol, propanol, iso-propanol, butanol, iso-butanol and tert-butanol.

Bases (deprotonating agents) which can be employed when carrying outprocess (B) according to the invention are all customary protonacceptors. The following can preferably be used: oxides, hydroxides andcarbonates of alkali metals and alkaline earth metals, such as sodiumhydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodiumcarbonate, potassium carbonate and calcium carbonate, all of which canalso be employed in the presence of phase transfer catalysts, such as,for example, triethylbenzyl ammonium chloride, tetrabutyl ammoniumbromide, Adogen 464 (=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris-(methoxyethoxyethyl)-amine). Alkali metals, such as sodium orpotassium, can furthermore be used. Other substances which can beemployed are amides and hydrides of alkali metals and alkaline earthmetals, such as sodium amide, sodium hydride and calcium hydride, andfurthermore also alkali metal alcoholates, such as sodium methoxide,sodium ethoxide and potassium tert-butoxide.

When carrying out process (B) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (B) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (B) according to the invention, the reactantsof the formula (III) and the deprotonating bases are generally employedin approximately equimolar amounts. However, it is also possible to useone or the other component in a larger excess (up to 3 mol).

Process (C) is characterized in that compounds of the formula (IV) inwhich A, B, V, W, X, Y and R⁸ have the abovementioned meanings aresubjected to an intramolecular cyclization in the presence of an acidand, if appropriate, in the presence of a diluent.

Diluents which can be employed in process (C) according to the inventionare all inert organic solvents. The following can preferably be used:hydrocarbons, such as toluene and xylene, furthermore halogenatedhydrocarbons, such as dichloromethane, chloroform, ethylene chloride,chlorobenzene, dichlorobenzene, moreover polar solvents, such asdimethyl sulphoxide, sulpholane, dimethylformamide andN-methyl-pyrrolidone. Other substances which can be employed arealcohols, such as methanol, ethanol, propanol, iso-propanol, butanol,isobutanol or tert-butanol.

If appropriate, the acid employed may also act as the diluent.

Acids which can be employed in process (C) according to the inventionare all customary inorganic and organic acids, such as, for example,hydrohalic acids, sulphuric acid, alkyl-, aryl- and haloalkylsulphonicacids, in particular halogenated alkylcarboxylic acids, such as, forexample, trifluoroacetic acid.

When carrying out process (C) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (C) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (C) according to the invention, the reactantsof the formula (IV) and the acid are employed, for example, in equimolaramounts. If appropriate, however, it is also possible to use the acid asthe solvent or the catalyst.

Process (D) according to the invention is characterized in that carbonylcompounds of the formula (V) or their enol ethers of the formula (V-a)are reacted with ketene acid halides of the formula (VI), in thepresence of a diluent and if appropriate in the presence of an acidacceptor.

Diluents which can be employed in process (D) according to the inventionare all inert organic solvents. The following can preferably be used:optionally halogenated hydrocarbons, such as toluene, xylene,mesitylene, chlorobenzene and dichlorobenzene, furthermore ethers, suchas dibutyl ether, glycol dimethyl ether, diglycol dimethyl ether anddiphenyl ether, furthermore polar solvents, such as dimethyl sulphoxide,sulpholane, dimethylformamide or N-methyl-pyrrolidone.

Acid acceptors which can be used for carrying out the process variant(D) according to the invention are all customary acid acceptors.

The following can preferably be used: tertiary amines, such astriethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecane (DBU), diazabicyclononene (DBN), Hünig base andN,N-dimethyl-aniline.

When carrying out process variant (D) according to the invention, thereaction temperatures can be varied within a substantial range. Theprocess is expediently carried out at temperatures between 0° C. and250° C., preferably between 50° C. and 220° C.

Process (D) according to the invention is expediently carried out underatmospheric pressure.

When carrying out process (D) according to the invention, the reactantsof the formulae (V) and (VI) in which A, D, W, X and Y have theabovementioned meanings and Hal represents halogen and, if appropriate,the acid acceptors are generally employed in approximately equimolaramounts. However, it is also possible to use one or another component ina larger excess (up to 5 mol).

Process (E) according to the invention is characterized in thatthioamides of the formula (VII) are reacted with ketene acid halides ofthe formula (VI), in the presence of a diluent and if appropriate in thepresence of an acid acceptor.

Diluents which can be employed in process variant (E) according to theinvention are all inert organic solvents. The following can preferablybe used: hydrocarbons, such as toluene and xylene, furthermore ethers,such as dibutyl ether, glycol dimethyl ether and diglycol dimethylether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane;dimethylformamide and N-methyl-pyrrolidone.

Acid acceptors which can be used for carrying out process (E) accordingto the invention are all customary acid acceptors.

The following can preferably be used: tertiary amines, such astriethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecane (DBU), diazabicyclononene (DBN), Hünig base andN,N-dimethyl-aniline.

When carrying out process (E) according to the invention, the reactiontemperatures can be varied within a substantial range. The process isexpediently carried out at temperatures between 0° C. and 250° C.,preferably between 20° C. and 220° C.

Process (E) according to the invention is expediently carried out underatmospheric pressure.

When carrying out process (E) according to the invention, the reactantsof the formulae (VII) and (VI) in which A, W, X and Y have theabovementioned meanings and Hal represents halogen, and, if appropriate,the acid acceptors, are generally employed in approximately equimolaramounts. However, it is also possible to use one or the other componentin a larger excess (up to 5 mol).

Process (F) is characterized in that compounds of the formula (VIII) inwhich A, B, Q¹, Q², W, X, Y and R⁸ have the abovementioned meanings aresubjected to an intramolecular condensation reaction in the presence ofa base.

Diluents which can be employed in process (F) according to the inventionare all organic solvents which are inert towards the reactants. Thefollowing can preferably be used: hydrocarbons such as toluene andxylene, furthermore ethers such as dibutyl ether, tetrahydrofuran,dioxane, glycol dimethyl ether and diglycol dimethyl ether, moreoverpolar solvents such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methylpyrrolidone. Alcohols such as methanol,ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol canalso be employed.

Bases (deprotonating agents) which can be employed when carrying outprocess (F) according to the invention are all customary protonacceptors. The following can preferably be used: the oxides, hydroxidesand carbonates of alkali metals and alkaline earth metals, such assodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide,sodium carbonate, potassium carbonate and calcium carbonate, all ofwhich can also be employed in the presence of phase transfer catalystssuch as, for example, triethylbenzylammonium chloride,tetrabutylammonium bromide, Adogen 464 (methyltrialkyl(C₈-C₁₀)ammoniumchloride) or TDA 1 (tris(methoxyethoxyethyl)-amine). Alkali metals suchas sodium or potassium may also be employed. Others which can beemployed are amides and hydrides of alkali metals and alkaline earthmetals, such as sodium amide, sodium hydride and calcium hydride, andfurthermore also alkali metal alcoholates such as sodium methoxide,sodium ethoxide and potassium tert-butoxide.

When carrying out process (F) according to the invention, the reactiontemperatures can be varied within a substantial range. The process isgenerally carried out at temperatures between −75° C. and 250° C.,preferably between −50° C. and 150° C.

Process (F) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (F) according to the invention, the reactantsof the formula (VIII) and the deprotonating bases are generally employedin approximately equimolar amounts. However, it is also possible to useone or the other component in a larger excess (up to 3 mol).

Process (G) is characterized in that compounds of the formula (IX) inwhich A, B, Q³, Q⁴, Q⁵, Q⁶, W, X, Y and R⁸ have the abovementionedmeanings are subjected to an intramolecular condensation reaction in thepresence of bases.

Diluents which can be employed in process (G) according to the inventionare all organic solvents which are inert towards the reactants. Thefollowing can preferably be used: hydrocarbons such as toluene andxylene, furthermore ethers such as dibutyl ether, tetrahydrofuran,dioxane, glycol dimethyl ether and diglycol dimethyl ether, moreoverpolar solvents such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methylpyrrolidone. Alcohols such as methanol,ethanol, propanol, iso-propanol, butanol, iso-butanol, tert-butanol canalso be employed.

Bases (deprotonating agents) which can be employed when carrying outprocess (G) according to the invention are all customary protonacceptors.

The following can preferably be used: the oxides, hydroxides andcarbonates of alkali metals and alkaline earth metals, such as sodiumhydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodiumcarbonate, potassium carbonate and calcium carbonate, all of which canalso be employed in the presence of phase transfer catalysts such as,for example, triethylbenzylammonium chloride, tetrabutylammoniumbromide, Adogen 464 (methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(tris(methoxy-ethoxyethyl)amine). Alkali metals such as sodium orpotassium may also be employed. Others which can be employed are amidesand hydrides of alkali metals and alkaline earth metals, such as sodiumamide, sodium hydride and calcium hydride, and furthermore also alkalimetal alcoholates such as sodium methoxide, sodium ethoxide andpotassium tert-butoxide.

When carrying out process (G) according to the invention, the reactiontemperatures can be varied within a substantial range. The process isgenerally carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (G) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (G) according to the invention, the reactantsof the formula (IX) and the deprotonating bases are generally employedin approximately equimolar amounts. However, it is also possible to useone or the other component in a larger excess (up to 3 mol).

Process (H-α) according to the invention is characterized in thathydrazines of the formula (X) or salts of these compounds are reactedwith ketene acid halides of the formula (VI) in the presence of adiluent and if appropriate in the presence of an acid acceptor.

Diluents which can be employed in process (H-α) according to theinvention are all inert organic solvents. The following can preferablybe used: optionally chlorinated hydrocarbons such as, for example,mesitylene, chlorobenzene and dichlorobenzene, toluene, xylene,furthermore ethers such as dibutyl ether, glycol dimethyl ether,diglycol dimethyl ether and diphenylethane, moreover polar solvents suchas dimethyl sulphoxide, sulpholane, dimethylformamide orN-methylpyrrolidone.

Acid acceptors which can be used for carrying out process variant (H-α)according to the invention are all customary acid acceptors.

The following can preferably be used: tertiary amines such astriethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecane (DBU), diazabicyclononene (DBN), Hünig base andN,N-dimethylaniline.

When carrying out the process variant (H-α) according to the invention,the reaction temperatures can be varied within a substantial range. Theprocess is expediently carried out at temperatures between 0° C. and250° C., preferably between 50° C. and 220° C.

Process (H-α) according to the invention is expediently carried outunder atmospheric pressure.

When carrying out process (H-α) according to the invention, thereactants of the formulae (VI) and (X) in which A, D, W, X and Y havethe abovementioned meanings and Hal represents halogen, and, ifappropriate, the acid acceptors, are generally employed in approximatelyequimolar amounts. However, it is also possible to use one or the othercomponent in a larger excess (up to 5 mol).

Process (H-β) is characterized in that hydrazines of the formula (X) orsalts of this compound in which A and D have the abovementioned meaningsare subjected to a condensation reaction with malonic esters ormalonamides of the formula (XI) in which U, W, X, Y and R⁸ have theabovementioned meanings in the presence of a base.

Diluents which can be employed in process (H-β) according to theinvention are all inert organic solvents. The following can preferablybe used: optionally halogenated hydrocarbons such as toluene, xylene,mesitylene, chlorobenzene and dichlorobenzene, furthermore ethers suchas dibutyl ether, tetrahydrofuran, dioxane, diphenyl ether, glycoldimethyl ether and diglycol dimethyl ether, moreover polar solvents suchas dimethyl sulphoxide, sulpholane, dimethylformamide, dimethylacetamideand N-methyl-pyrrolidone, and alcohols such as methanol, ethanol,propanol, iso-propanol, butanol, iso-butanol and tert-butanol.

Bases (deprotonating agents) which can be employed when carrying outprocess (H-β) according to the invention are all customary protonacceptors. The following can preferably be used: oxides, hydroxides andcarbonates of alkali metals and alkaline earth metals, such as sodiumhydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodiumcarbonate, potassium carbonate and calcium carbonate, all of which canalso be employed in the presence of phase transfer catalysts such as,for example, tri-ethylbenzylammonium chloride, tetrabutylammoniumbromide, Adogen 464 (=methyl-trialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris(methoxyethoxyethyl)amine). Others which can be used are alkalimetals such as sodium or potassium. Amides and hydrides of alkali metalsand alkaline earth metals, such as sodium amide, sodium hydride andcalcium hydride, and moreover also alkali metal alcoholates, such assodium methoxide, sodium ethoxide and potassium tert-butoxide, can alsobe employed.

Others which can be employed are tertiary amines such as triethylamine,pyridine, diazabicyclooctane (DABCO), diazabicycloundecane (DBU),diazabicyclononene (DBN), Hünig base and N,N-dimethylaniline.

When carrying out process (H-β) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 280° C.,preferably between 50° C. and 180° C.

Process (H-β) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (H-β) according to the invention, thereactants of the formulae (XI) and (X) are generally employed inapproximately equimolar amounts. However, it is also possible to use oneor the other component in a larger excess (up to 3 mol).

Process (H-γ) is characterized in that compounds of the formula (XII) inwhich A, D, W, X, Y and R⁸ have the abovementioned meanings aresubjected to an intramolecular condensation reaction in the presence ofa base.

Diluents which can be employed in process (H-γ) according to theinvention are all inert organic solvents. The following can preferablybe used: hydrocarbons such as toluene and xylene, furthermore etherssuch as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl etherand diglycol dimethyl ether, moreover polar solvents such as dimethylsulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone, andalcohols such as methanol, ethanol, propanol, iso-propanol, butanol,iso-butanol and tert-butanol.

Bases (deprotonating agents) which can be employed when carrying outprocess (H-γ) according to the invention are all customary protonacceptors. The following can preferably be used: oxides, hydroxides andcarbonates of alkali metals and alkaline earth metals, such as sodiumhydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodiumcarbonate, potassium carbonate and calcium carbonate, all of which canalso be employed in the presence of phase transfer catalysts such as,for example, triethylbenzylammonium chloride, tetrabutylammoniumbromide, Adogen 464 (=methyl-trialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris(methoxyethoxyethyl)amine). Others which can be used are alkalimetals such as sodium or potassium. Amides and hydrides of alkali metalsand alkaline earth metals, such as sodium amide, sodium hydride andcalcium hydride, and moreover also alkali metal alcoholates, such assodium methoxide, sodium ethoxide and potassium tert-butoxide, can alsobe employed.

When carrying out process (H-γ) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (H-γ) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (H-γ) according to the invention, thereactants of the formula (XII) and the deprotonating bases are generallyemployed in approximately twice the molar amounts. However, it is alsopossible to employ one or the other component in a larger excess (up to3 mol).

Process (I-α) is characterized in that compounds of the formulae (I-1-a)to (I-8-a) are reacted in each case with carboxylic acid halides of theformula (XIII), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid-binding agent.

Diluents which can be employed in process (I-α) according to theinvention are all solvents which are inert to the acid halides. Thefollowing can preferably be used: hydrocarbons, such as benzine,benzene, toluene, xylene and tetralin, furthermore halogenohydrocarbons,such as methylene chloride, chloroform, carbon tetrachloride,chlorobenzene and o-dichlorobenzene, moreover ketones, such as acetoneand methyl isopropyl ketone, furthermore ethers, such as diethyl ether,tetrahydrofuran and dioxane, in addition carboxylic esters, such asethyl acetate, and also strongly polar solvents, such as dimethylsulphoxide and sulpholane. If the acid halide is sufficiently stable tohydrolysis, the reaction can also be carried out in the presence ofwater.

Suitable acid-binding agents in the reaction in accordance with process(I-α) according to the invention are all customary acid acceptors. Thefollowing can preferably be used: tertiary amines, such astriethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecane (DBU), diazabicyclononene (DBN), Hünig base andN,N-dimethyl-aniline, furthermore alkaline earth metal oxides, such asmagnesium oxide and calcium oxide, moreover alkali metal carbonates andalkaline earth metal carbonates, such as sodium carbonate, potassiumcarbonate and calcium carbonate, and also alkali metal hydroxides, suchas sodium hydroxide and potassium hydroxide.

The reaction temperatures in process (I-α) according to the inventioncan be varied within a substantial range. In general, the process iscarried out at temperatures between −20° C. and +150° C., preferablybetween 0° C. and 100° C.

When carrying out process (I-α) according to the invention, the startingsubstances of the formulae (I-1-a) to (I-8-a) and the carboxylic acidhalide of the formula (XIII) are generally used in approximatelyequivalent amounts in each case. However, it is also possible to employthe carboxylic acid halide in a larger excess (up to 5 mol). Working-upis carried out by customary methods.

Process (I-β) is characterized in that compounds of the formulae (I-1-a)to (I-8-a) are reacted with carboxylic anhydrides of the formula (XIV),if appropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent.

Diluents which can preferably be used in process (I-β) according to theinvention are those which are also preferably suitable when using acidhalides. Besides, a carboxylic anhydride employed in excess may alsosimultaneously act as the diluent.

Optionally added acid-binding agents in process (I-β) are preferablythose acid-binding agents which are also preferably suitable when usingacid halides.

The reaction temperatures in process (I-β) according to the inventioncan be varied within a substantial range. In general, the process iscarried out at temperatures between −20° C. and +150° C., preferablybetween 0° C. and 100° C.

When carrying out process (I-β) according to the invention, the startingsubstances of the formulae (I-1-a) to (I-8-a) and the carboxylicanhydride of the formula (XIV) are generally employed in each case inapproximately equivalent amounts. However, it is also possible to employthe carboxylic anhydride in a larger excess (up to 5 mol). Working-up iscarried out by customary methods.

In general, a procedure is followed in which diluent and carboxylicanhydride which is present in excess and the carboxylic acid which formsare removed by distillation or by washing with an organic solvent orwith water.

Process (J) is characterized in that compounds of the formulae (I-1-a)to (I-8-a) are reacted in each case with chloroformic esters orchloroformic thioesters of the formula (XV), if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

Suitable acid-binding agents for the reaction in accordance with process(J) according to the invention are all customary acid acceptors. Thefollowing can preferably be used: tertiary amines, such astriethylamine, pyridine, DABCO, DBU, DBA, Hünig base andN,N-dimethyl-aniline, furthermore alkaline earth metal oxides, such asmagnesium oxide and calcium oxide, moreover alkali metal carbonates andalkaline earth metal carbonates, such as sodium carbonate, potassiumcarbonate and calcium carbonate, and also alkali metal hydroxides, suchas sodium hydroxide and potassium hydroxide.

Diluents which can be employed in process (J) according to the inventionare all solvents which are inert to the chloroformic esters orchloroformic thioesters. The following can preferably be used:hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin,furthermore halogenohydrocarbons, such as methylene chloride,chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene,moreover ketones, such as acetone and methyl isopropyl ketone,furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane,additionally carboxylic esters, such as ethyl acetate, and also stronglypolar solvents, such as dimethyl sulphoxide and sulpholane.

When carrying out process (J) according to the invention, the reactiontemperatures can be varied within a substantial range. If the process iscarried out in the presence of a diluent and of an acid-binding agent,the reaction temperatures are generally between −20° C. and +100° C.,preferably between 0° C. and 50° C.

Process (J) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (J) according to the invention, the startingsubstances of the formulae (I-1-a) to (I-8-a) and the respectivechloroformic ester or chloroformic thioester of the formula (XIII) aregenerally used in in each case approximately equivalent amounts.However, it is also possible to employ one or the other component in alarger excess (up to 2 mol). Working-up is carried out by customarymethods. In general, a procedure is followed in which salts which haveprecipitated are removed and the reaction mixture which remains isconcentrated by stripping off the diluent.

Process (K) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-8-a) are reacted in each casewith compounds of the formula (XVI) in the presence of a diluent and, ifappropriate, in the presence of an acid-binding agent.

In preparation process (K), approximately 1 mol of chloromonothioformicester or chlorodithioformic ester of the formula (XVI) is reacted permole of starting compound of the formulae (I-1-a) to (I-8-a) at 0 to120° C., preferably at 20 to 60° C.

Suitable diluents which are optionally added are all inert polar organicsolvents, such as ethers, amides, sulphones, sulphoxides, but alsohalogenoalkanes.

Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylenechloride are preferably employed.

If, in a preferred embodiment, the enolate salt of the compounds (I-1-a)to (I-8-a) is prepared by adding strong deprotonating agents, such as,for example, sodium hydride or potassium tertiary-butoxide, the furtheraddition of acid-binding agents can be dispensed with.

If acid-binding agents are employed, then suitable substances arecustomary inorganic or organic bases, examples which may be mentionedbeing sodium hydroxide, sodium carbonate, potassium carbonate; pyridineand triethylamine.

The reaction can be carried out under atmospheric pressure or underelevated pressure, it is preferably carried out under atmosphericpressure. Working-up is carried out by customary methods.

Process (L) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-8-a) are reacted in each casewith sulphonyl chlorides of the formula (XVII), if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

In preparation process (L), approximately 1 mol of sulphonyl chloride ofthe formula (XVII) is reacted per mole of starting compound of theformulae (I-1-a) to (I-8-a) at −20 to 150° C., preferably at 20 to 70°C.

Suitable diluents which are optionally added are all inert polar organicsolvents, such as ethers, amides, nitriles, sulphones, sulphoxides, orhalogenated hydrocarbons, such as methylene chloride.

Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylenechloride are preferably employed.

If, in a preferred embodiment, the enolate salt of the compounds (I-1-a)to (I-8-a) is prepared by adding strong deprotonating agents (such as,for example, sodium hydride or potassium tertiary-butoxide), the furtheraddition of acid-binding agents can be dispensed with.

If acid-binding agents are employed, then suitable substances arecustomary inorganic or organic bases, examples which may be mentionedbeing sodium hydroxide, sodium carbonate, potassium carbonate, pyridineand triethylamine.

The reaction can be carried out under atmospheric pressure or underelevated pressure, it is preferably carried out under atmosphericpressure. Working-up is carried out by customary methods.

Process (M) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-8-a) are reacted in each casewith phosphorus compounds of the formula (XVIII), if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

In preparation process (M), 1 to 2, preferably 1 to 1.3, mol of thephosphorus compound of the formula (XVIII) are reacted per mole of thecompounds (I-1-a) to (I-8-a) at temperatures between −40° C. and 150°C., preferably between −10 and 110° C., to obtain compounds of theformulae (I-1-e) to (I-8-c).

Suitable diluents which are optionally added are all inert, polarorganic solvents, such as ethers, amides, nitriles, alcohols, sulphides,sulphones, sulphoxides and the like.

Acetonitrile, dimethyl sulphoxide, tetrahydrofuran, dimethylformamide ormethylene chloride are preferably employed.

Suitable acid-binding agents which are optionally added are customaryinorganic or organic bases, such as hydroxides, carbonates or amines.Examples which may be mentioned are sodium hydroxide, sodium carbonate,potassium carbonate, pyridine and triethylamine.

The reaction can be carried out under atmospheric pressure or underelevated pressure, it is preferably carried out under atmosphericpressure. Working-up is carried out by customary methods of organicchemistry. The end products obtained are preferably purified bycrystallization, chromatography or by so-called “incipientdistillation”, i.e. removal of the volatile components in vacuo.

Process (N) is characterized in that compounds of the formulae (I-1-a)to (I-8-a) are reacted with metal hydroxides or metal alkoxides of theformula (XIX) or amines of the formula (XX), if appropriate in thepresence of a diluent.

Diluents which can be employed in process (N) according to the inventionare, preferably, ethers, such as tetrahydrofuran, dioxane, diethylether, or else alcohols, such as methanol, ethanol, isopropanol, butalso water.

Process (N) according to the invention is generally carried out underatmospheric pressure.

The reaction temperatures are generally between −20° C. and 100° C.,preferably between 0° C. and 50° C.

Process (O) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-8-a) are reacted in each casewith (O-α) compounds of the formula (XXI), if appropriate in thepresence of a diluent and if appropriate in the presence of a catalyst,or (O-β) with compounds of the formula (XXII), if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

In preparation process (O-α), approximately 1 mol of isocyanate of theformula (XXI) is reacted per mole of starting compound of the formulae(I-1-a) to (I-8-a) at 0 to 100° C., preferably at 20 to 50° C.

Suitable diluents which are optionally added are all inert organicsolvents, such as ethers, amides, nitriles, sulphones or sulphoxides.

If appropriate, catalysts may be added to accelerate the reaction.Catalysts which can be employed very advantageously are organotincompounds, such as, for example, dibutyltin dilaurate. The process ispreferably carried out under atmospheric pressure.

In preparation process (O-β), approximately 1 mol of carbamoyl chlorideof the formula (XXII) is reacted per mole of starting compound of theformulae (I-1-a) to (I-8-a) at −20 to 150° C., preferably at 0 to 70° C.

The diluents which are optionally added are all inert polar organicsolvents, such as ethers, amides, sulphones, sulphoxides or halogenatedhydrocarbons.

Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylenechloride are preferably employed.

If, in a preferred embodiment, the enolate salt of the compound (I-1-a)to (I-8-a) is prepared by adding strong deprotonating agents (such as,for example, sodium hydride or potassium tertiary-butoxide), the furtheraddition of acid-binding agents can be dispensed with.

If acid-binding agents are employed, then suitable substances arecustomary inorganic or organic bases, examples which may be mentionedbeing sodium hydroxide, sodium carbonate, potassium carbonate,triethylamine or pyridine.

The reaction can be carried out under atmospheric pressure or underelevated pressure, it is preferably carried out under atmosphericpressure. Working-up is carried out by customary methods.

Process (P) is characterized in that compounds of the formulae (I-1-a′)to (I-8-a′) in which A, B, D, Q¹, Q², Q³, Q⁴, Q⁵, Q⁶, X and Y have theabovementioned meanings and W′ preferably represents bromine are reactedwith alcohols of the formula WOH in which W has the abovementionedmeaning, in the presence of a base and of a Cu(I) salt (for example CuBror CuI).

Diluents which can be employed in process (P) according to the inventionare all organic solvents which are inert to the reactants. The followingcan preferably be used: hydrocarbons such as toluene and xylene,furthermore ethers such as dibutyl ether, tetrahydrofuran, dioxane,glycol dimethyl ether and diglycol dimethyl ether, moreover polarsolvents such as dimethyl sulphoxide, sulpholane, dimethylformamide,dimethylacetamide and N-methylpyrrolidone, esters such as methylacetate, ethyl acetate, propyl acetate, and alcohols of the formula WOHsuch as, for example, methanol, ethanol, propanol, iso-propanol, butanoland iso-butanol.

Bases (deprotonating agents) which can be employed for carrying outprocess (P) according to the invention are all customary protonacceptors. Alkali metals such as sodium or potassium can preferably beused. Others which can be employed are amides and hydrides of alkalimetals and alkaline earth metals, such as sodium amide, sodium hydrideand calcium hydride, and preferably also alkali metal alcoholates suchas sodium methoxide, sodium ethoxide, sodium isopropoxide, sodiumtert-butoxide and potassium tert-butoxide.

When carrying out process (P) according to the invention, the reactiontemperature can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (P) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (P) according to the invention, the reactantsof the formulae (I-1-a′) to (I-8-a′) are generally reacted with anexcess of the alcohols WOH and of the bases of up to 20 mol, preferably3 to 5 mol. As a rule, the copper(1) salts are employed in catalyticamounts of 0.001 to 0.5 mol, preferably 0.01 to 0.2 mol. However, theymay also be employed in equimolar amounts.

The active compounds are well tolerated by plants, have advantageoustoxicity to warm-blooded species and are environmentally friendly; theycan be employed for protecting plants and plant organs, for increasingyields, improving crop quality and for controlling animal pests, inparticular insects, arachnids and nematodes found in agriculture,forests, gardens and leisure grounds, in the protection of storedproducts and materials and in the hygiene sector. They can be used withpreference to protect plants. They are active against normally sensitiveand resistant species and against all or some stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp.,

Locusta migratoria migratorioides, Melanoplus spp. and Schistocercagregaria.

From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae and Blattella germanica.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp.,Damalinia spp.

From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcomi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example; Pectinophoragossypiella, Bupalus piniarius, Chematobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp. and Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica and Lissorphoptrusoryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp. and Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp. and Brevipalpus spp.

The plant-parasitic nematodés include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchusspp.

If appropriate, the compounds according to the invention may also beused in certain concentrations or application rates to act as herbicidesand microbicides, for example as fungicides, antimycotics andbactericides. If appropriate, they can also be employed as intermediatesor precursors for the synthesis of further active compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (including naturally occurring crop plants). Cropplants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, including the transgenicplants and inclusive of the plant cultivars protectable or notprotectable by plant breeders' rights. Plant parts are to be understoodas meaning all parts and organs of plants above and below the ground,such as shoot, leaf, flower and root, examples which may be mentionedbeing leaves, needles, stalks, stems, flowers, fruit bodies, fruits,seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offsets and seeds.

The treatment according to the invention of the plants and plant partswith the active compounds is carried out directly or by allowing thecompounds to act on the surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on or injection and, in thecase of propagation material, in particular in the case of seeds, alsoby applying one or more coats.

The active compounds can be converted into the customary formulationssuch as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and microencapsulations in polymeric materials.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents and/orsolid carriers, optionally with the use of surfactants, that is,emulsifiers and/or dispersants, and/or foam formers.

If the extender used is water, it is also possible, for example, to useorganic solvents as cosolvents. The following are essentially suitableas liquid solvents: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic materials such as highly-disperse silica,alumina and silicates; suitable solid carriers for granules are: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, or else synthetic granules of inorganicand organic meals, and granules of organic material such as sawdust,coconut shells, maize cobs and tobacco stalks; suitable emulsifiersand/or foam formers are: for example nonionic and anionic emulsifierssuch as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates, or else protein hydrolysates; suitabledispersants are: for example lignin-sulphite waste liquors andmethylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic colorants suchalizarin colorants, azo colorants and metal phthalocyanine colorants,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in theirformulations, can also be used as a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, for example inorder to widen the spectrum of action or to prevent the development ofresistances in this way. In many cases, synergistic effects result, i.e.the activity of the mixture exceeds the activity of the individualcomponents.

Compounds which are suitable as components in the mixtures are, forexample, the following:

Fungicides:

2-phenylphenol; 8-hydroxyquinoline sulphate; acibenzolar-5-methyl;aldimorph; amidoflumet; ampropylfos; ampropylfos-potassium; andoprim;anilazine; azaconazole; azoxystrobin; benalaxyl; benodanil; benomyl;benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; bilanafos;binapacryl; biphenyl; bitertanol; blasticidin-S; bromuconazole;bupirimate; buthiobate; butylamine; calcium polysulphide; capsimycin;captafol; captan; carbendazim; carboxin; carpropamid; carvone;quinomethionate; chlobenthiazone; chlorfenazole; chloroneb;chlorothalonil; chlozolinate; clozylacon; cyazofamid; cyflufenamid;cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G; debacarb;dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine;dicloran; diethofencarb; difenoconazole; diflumetorim; dimethirimol;dimethomorph; dimoxystrobin; diniconazole; diniconazole-M; dinocap;diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; drazoxolon;edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole;famoxadone; fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram;fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin;fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil; flumetover;flumorph; fluoromide; fluoxastrobin; fluquinconazole; flurprimidol;flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl-Al;fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil;furmecyclox; guazatine; hexachlorobenzene; hexaconazole; hymexazol;imazalil; imibenconazole; iminoctadine triacetate; iminoctadinetris(albesilate); iodocarb; ipconazole; iprobenfos; iprodione;iprovalicarb; irumamycin; isoprothiolane; isovaledione; kasugamycin;kresoxim-methyl; mancozeb; maneb; meferimzone; mepanipyrim; mepronil;metalaxyl; metalaxyl-M; metconazole; methasulfocarb; methfuroxam;metiram; metominostrobin; metsulfovax; mildiomycin; myclobutanil;myclozolin; natamycin; nicobifen; nitrothal-isopropyl; noviflumuron;nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole;oxycarboxin; oxyfenthiin; paclobutrazol; pefurazoate; penconazole;pencycuron; phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins;polyoxorim; probenazole; prochloraz; procymidone; propamocarb;propanosine-sodium; propiconazole; propineb; proquinazid;prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil;pyroquilon; pyroxyfur; pyrrolnitrin; quinconazole; quinoxyfen;quintozene; simeconazole; spiroxamine; sulphur; tebuconazole;tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabendazole;thicyofen; thifluzamide; thiophanate-methyl; thiram; tioxymid;tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; triazbutil;triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin;triflumizole; triforine; triticonazole; uniconazole; validamycin A;vinclozolin; zineb; ziram; zoxamide;(2S)—N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulphonyl)amino]-butanamide;1-(1-naphthalenyl)-1H-pyrrole-2,5-dione;2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine;2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide;2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide;3,4,5-trichloro-2,6-pyridinedicarbonitrile; Actinovate;cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazole-1-yl)-cycloheptanol; methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate;monopotassium carbonate;N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide;N-butyl-8-(1,1-dimethylethyl)-1-oxaspiro[4,5]decan-3-amine; sodiumtetrathiocarbonate;and copper salts and preparations such as Bordeaux mixture; copperhydroxide; copper naphthenate; copper oxychloride; copper sulfate;cufraneb; cuprous oxide; mancopper, oxine-copper.

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, ABG-9008, acephate, acequinocyl, acetamiprid, acetoprole,acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb, aldicarb,aldoxycarb, allethrin, alpha-cypermethrin (alphamethrin), amidoflumet,aminocarb, amitraz, avermectin, AZ-60541, azadirachtin, azamethiphos,azinphos-methyl, azinphos-ethyl, azocyclotin, Bacillus popilliae,Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillusthuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91,Bacillus thuringiensis strain NCTC-11821, baculoviruses, Beauveriabassiana, Beauveria tenella, benclothiaz, bendiocarb, benfuracarb,bensultap, benzoximate, beta-cyfluthrin, beta-cypennethrin, bifenazate,bifenthrin, binapacryl, bioallethrin, bioallethrin S-cyclopentyl isomer,bioethanomethrin, biopermethrin, bioresmethrin, bistrifluoron, BPMC,brofenprox, bromophos-ethyl, bromopropylate, bromfenvinfos (-methyl),BTG-504, BTG-505, bufencarb, buprofezin, butathiofos, butocarboxim,butoxycarboxim, butylpyridaben,cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion,carbosulfan, cartap, CGA-50439, quinomethionate, chlordane,chlordimeform, chloethocarb, chlorethoxyfos, chlorfenapyr,chlorfenvinphos, chlorfluazuron, chlormephos, chlorobenzilate,chloropicrin, chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl),chlovaporthrin, chromafenozide, cis-cypermethrin, cis-resmethrin,cis-permethrin, clocythrin, cloethocarb, clofentezine, clothianidin,clothiazoben, codlemone, coumaphos, cyanofenphos, cyanophos, cycloprene,cycloprothrin, Cydia pomonella, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyphenothrin (1R-trans isomer), cyromazine,DDT, deltamethrin, demeton-S-methyl, demeton-S-methylsulphone,diafenthiuron, dialifos, diazinon, dichlofenthion, dichlorvos, dicofol,dicrotophos, dicyclanil, diflubenzuron, dimefluthrin, dimethoate,dimethylvinphos, dinobuton, dinocap, dinotefuran, diofenolan,disulfoton, docusate-sodium, dofenapyn, DOWCO-439,eflusilanate, emamectin, emamectin benzoate, empenthrin (1R isomer),endosulfan, Entomophthora spp., EPN, esfenvalerate, ethiofencarb,ethiprole, ethion, ethoprophos, etofenprox, etoxazole, etrimfos,famphur, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin,fenitrothion, fenobucarb, fenothiocarb, fenoxacrim, fenoxycarb,fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fensulfothion,fenthion, fentrifanil, fenvalerate, fipronil, flonicamid, fluacrypyrim,fluazuron, flubenzimine, flubrocythrinate, flucycloxuron, flucythrinate,flufenerim, flufenoxuron, flufenprox, flumethrin, flupyrazofos,flutenzin (flufenzine), fluvalinate, fonofos, formetanate, formothion,fosmethilan, fosthiazate, fubfenprox (fluproxyfen), furathiocarb,gamma-cyhalothrin, gamma-HCH, gossyplure, grandlure, granulosis viruses,halfenprox, halofenozide, HCH, HCN-801, heptenophos, hexaflumuron,hexythiazox, hydramethylnone, hydroprene,IKA-2002, imidacloprid, imiprothrin, indoxacarb, iodofenphos,iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin,japonilure,kadethrin, nuclear polyhedrosis viruses, kinoprene,lambda-cyhalothrin, lindane, lufenuron,malathion, mecarbam, mesulfenfos, metaldehyde, metam-sodium,methacrifos, methamidophos, Metarhizium anisopliae, Metarhiziumflavoviride, methidathion, methiocarb, methomyl, methoprene,methoxychlor, methoxyfenozide, metofluthrin, metolcarb, metoxadiazone,mevinphos, milbemectin, milbemycin, MKI-245, MON-45700, monocrotophos,moxidectin, MTI-800,naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide, nicotine,nitenpyram, nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768,novaluron, noviflumuron,OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate, oxamyl,oxydemeton-methyl,Paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl),permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (1R-transisomer), phenthoate, phorate, phosalone, phosmet, phosphamidon,phosphocarb, phoxim, piperonyl butoxide, pirimicarb, pirimiphos-methyl,pirimiphos-ethyl, potassium oleate, prallethrin, profenofos,profluthrin, promecarb, propaphos, propargite, propetamphos, propoxur,prothiofos, prothoate, protrifenbute, pymetrozine, pyraclofos,pyresmethrin, pyrethrum, pyridaben, pyridalyl, pyridaphenthion,pyridathion, pyrimidifen, pyriproxyfen,quinalphos,resmethrin, RH-5849, ribavirin, RU-12457, RU-15525,S-421, S-1833, salithion, sebufos, SI-0009, silafluofen, spinosad,spirodiclofen, spiromesifen, sulfluramid, sulfotep, sulprofos, SZI-121,tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos,teflubenzuron, tefluthrin, temephos, Temivinphos, Terbam, Terbufos,Tetrachlorvinphos, Tetradifon, Tetra-methrin, Tetramethrin (1R isomer),tetrasul, theta-cypermethrin, thiacloprid, thiamethoxam, thiapronil,thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox,thiometon, thiosultap-sodium, thuringiensin, tolfenpyrad, tralocythrin,tralomethrin, transfluthrin, triarathene, triazamate, triazophos,triazuron, trichlophenidine, trichlorfon, Trichoderma atroviride,triflumuron, trimethacarb,vamidothion, vaniliprole, verbutin, Verticillium lecanii,

WL-108477, WL-40027, YI-5201, YI-5301, YI-5302,

XMC, xylylcarb,ZA-3274, zeta-cypermethrin, zolaprofos, ZXI-8901,the compound 3-methylphenyl propylcarbamate (Tsumacide Z),the compound3-(5-chloro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]octane-3-carbonitrile(CAS Reg. No. 185982-80-3) and the corresponding 3-endo isomer (CAS Reg.No. 185984-60-5) (cf. WO 96/37494, WO 98/25923),and preparations which contain insecticidally active plant extracts,nematodes, fungi or viruses.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators, safeners or semichemicals is alsopossible.

When used as insecticides in their commercially available formulationsand in the use forms prepared with these formulations, the activecompounds according to the invention can furthermore exist in the formof a mixture with synergists. Synergists are compounds by which theactivity of the active compounds is increased without it being necessaryfor the synergist added to be active itself.

When employed as insecticides, the active compounds can be present, intheir commercially available formulations and in the use forms preparedfrom these formulations, as a mixture with inhibitors, which reduce thedegradation of the active compound post-application in the plant'senvironment, on the surface of plant parts or in plant tissues.

The active compound content of the use forms prepared from thecommercially available formulations can vary within broad ranges. Theactive compound concentration of the use forms can be from 0.0000001 upto 95% by weight of active compound, preferably between 0.001 and 1% byweight.

They are applied in a customary manner adapted to suit the use forms.

As already mentioned above, it is possible to treat all plants or theirparts in accordance with the invention. In a preferred embodiment, wildplant species or plant varieties and plant cultivars which have beenobtained by traditional biological breeding methods, such ashybridization or protoplast fusion, and the parts of these varieties andcultivars are treated. In a further preferred embodiment, transgenicplants and plant cultivars which have been obtained by recombinantmethods, if appropriate in combination with conventional methods(genetically modified organisms), and their parts are treated. The term“parts” or “parts of plants” or “plant parts” has been explained above.

Plants which are treated particularly preferably in accordance with theinvention are those of the plant cultivars which are in each casecommercially available or in use. Plant cultivars are understood asmeaning plants with new traits which have been bred either byconventional breeding, by mutagenesis or by recombinant DNA techniques.They may take the form of cultivars, biotypes and genotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, nutrition), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widened activity spectrum and/or an increase in the activity ofthe substances and compositions which can be used in accordance with theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to salinity in the wateror soil, increased flowering performance, facilitated harvesting,accelerated maturation, higher yields, higher quality and/or betternutritional value of the harvested products, better storagecharacteristics and/or processability of the harvested products arepossible which exceed the effects which were actually to be expected.

The preferred transgenic plants or plant cultivars (those obtained byrecombinant methods) to be treated in accordance with the inventioninclude all those plants which, owing to the process of recombinantmodification, were given genetic material which confers particular,advantageous, valuable traits to these plants. Examples of suchproperties are better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to salinity in the wateror soil, increased flowering performance, facilitated harvesting,accelerated maturation, higher yields, higher quality and/or highernutritional value of the harvested products, better storagecharacteristics and/or better processability of the harvested products.Further examples of such traits, examples which must be mentionedespecially, are better defence of the plants against animal andmicrobial pests, such as against insects, mites, phytopathogenic fungi,bacteria and/or viruses and an increased tolerance of the plants tocertain herbicidal active compounds. Examples of transgenic plants whichmay be mentioned are the important crop plants, such as cereals (wheat,rice), maize, soybeans, potato, cotton, tobacco, oilseed rape and fruitplants (with the fruits apples, pears, citrus fruits and grapes), withparticular emphasis on maize, soybeans, potatoes, cotton, tobacco andoilseed rape. Traits which are especially emphasized are the increaseddefence of the plants against insects, arachnids, nematodes and slugsowing to toxins being formed in the plants, in particular toxins whichare generated in the plants by the genetic material of Bacillusthuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c),CryIIA, CryIIIBA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and theircombinations; hereinbelow “Bt plants”). Other traits which areparticularly emphasized are the increased defence of plants againstfungi, bacteria and viruses by the systemic acquired resistance (SAR),systemin, phytoalexins, elicitors and resistance genes andcorrespondingly expressed proteins and toxins. Other traits which areespecially emphasized are the increased tolerance of the plants tocertain herbicidal active compounds, for example imidazolinones,sulphonylureas, glyphosate or phosphinotricin (for example “PAT” gene).The genes which confer the desired traits in each case may also bepresent in the transgenic plants in combination with one another.Examples of “Bt plants” which may be mentioned are maize cultivars,cotton cultivars, soybean cultivars and potato cultivars which arecommercially available under the trade names YIELD GARD® (for examplemaize, cotton, soybeans), KnockOut® (for example maize), StarLink® (forexample maize) Bollgard® (cotton), Nucotn® (cotton) and NewLeaf®(potato). Examples of herbicide-tolerant plants which may be mentionedare maize cultivars, cotton cultivars and soybean cultivars which arecommercially available under the trade names Roundup Ready® (toleranceto glyphosate, for example maize, cotton, soybean) Liberty Link®(tolerance to phosphinothricin, for example oilseed rape IMI® (toleranceto imidazolinones) and STS® (tolerance to sulphonylureas, for examplemaize). Herbicide-resistant plants (plants bred in a conventional mannerfor herbicide tolerance) which may be mentioned include also thevarieties commercially available under then name Clearfield® (forexample maize). Naturally, these statements also apply to plantcultivars having these genetic traits or genetic traits still to bedeveloped, which plant cultivars will be developed and/or marketed inthe future.

The plants listed can be treated particularly advantageously inaccordance with the invention with the compounds of the general formulaI or the active compound mixtures according to the invention. Thepreferred ranges stated above for the active compounds and mixtures alsoapply to the treatment of these plants. Particularly emphasis may begiven to the treatment of plants with the compounds or mixturesspecifically mentioned in the present text.

The active compounds according to the invention are not only activeagainst plant, hygiene and stored-product pests, but also, in theveterinary medicine sector, against animal parasites (ectoparasites),such as ixodid ticks, argasid ticks, scab mites, trombiculid mites,flies (stinging and sucking), parasitic fly larvae, lice, hair lice,bird lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the sub-orders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

From the order of the Diptera and the sub-orders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopyslla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattella germanica and Supella spp.

From the sub-class of the Acari (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma app., Boophilus spp., Dermacentor spp.,Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp, Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp, Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds of the formula (I) according to the invention arealso suitable for combating arthropods which attack agriculturallivestock, such as, for example, cattle, sheep, goats, horses, pigs,donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese,honeybees, other domestic animals, such as, for example, dogs, cats,cage birds, aquarium fish, and so-called experimental animals, such as,for example, hamsters, guinea-pigs, rats and mice. By combating thesearthropods, it is intended to reduce deaths and decreased performances(in meat, milk, wool, hides, eggs, honey and the like), so that moreeconomical and simpler animal keeping is made possible by using theactive compounds according to the invention.

In the veterinary sector, the active compounds according to theinvention are used in a known manner by enteral administration, forexample in the form of tablets, capsules, drinks, drenches, granules,pastes, boli, the feed-through method, suppositories, by parenteraladministration, such as, for example, by means of injections(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal application, by dermal administration, forexample in the form of dipping or bathing, spraying, pouring-on andspotting-on, washing, dusting, and with the aid of shaped articles whichcomprise active compound, such as collars, ear tags, tail marks, limbbands, halters, marking devices and the like.

When administered to livestock, poultry, domestic animals and the like,the active compounds of the formula (I) can be used as formulations (forexample powders, emulsions, flowables) which comprise the activecompounds in an amount of 1 to 80%, either directly or after dilution bya factor of 100 to 10 000, or they may be used in the form of a chemicalbath.

Furthermore, it has been found that the compounds according to theinvention have a potent insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned by way of example and as beingpreferred, but without any limitation:

Beetles, such as

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Emobius mollis,Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis,Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus,Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec.,Dinoderus minutus.

Dermapterans, such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites, such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis,Coptotermes formosanus.

Bristletails, such as Lepisma saccharina.

Industrial materials are to be understood as meaning, in the presentcontext, non-live materials, such as, preferably, synthetic materials,glues, sizes, paper and board, leather, wood and timber products, andpaint.

The materials to be very particularly preferably protected againstattack by insects are wood and timber products.

Wood and timber products which can be protected by the compositionaccording to the invention or mixtures comprising such a composition areto be understood as meaning, for example:

construction timber, wooden beams, railway sleepers, bridge components,jetties, wooden vehicles, boxes, pallets, containers, telephone poles,wood cladding, windows and doors made of wood, plywood, particle board,joiner's articles, or wood products which, quite generally, are used inthe construction of houses or in joinery.

The active compounds can be used as such, in the form of concentrates orgenerally customary formulations, such as powders, granules, solutions,suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersant and/or binder or fixative, waterrepellent, if appropriate desiccants and UV stabilizers and, ifappropriate, colorants and pigments and other processing auxiliaries.

The insecticidal compositions or concentrates used for the protection ofwood and wooden materials comprise the active compound according to theinvention at a concentration of 0.0001 to 95% by weight, in particular0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thespecies and the occurrence of the insects and on the medium. The optimumrate of application can be determined upon use in each case by a testseries. However, in general, it suffices to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound, basedon the material to be protected.

The solvent and/or diluent used is an organochemical solvent or solventmixture and/or an oily or oil-type organochemical solvent or solventmixture of low volatility and/or a polar organochemical solvent orsolvent mixture and/or water and, if appropriate, an emulsifier and/orwetting agent.

Organochemical solvents which are preferably employed are oily oroil-type solvents having an evaporation number of above 35 and aflashpoint of above 30° C., preferably above 45° C. Substances which areused as such oily and oil-type solvents which have low volatility andare insoluble in water are suitable mineral oils or their aromaticfractions, or mineral-oil-containing solvent mixtures, preferably whitespirit, petroleum and/or alkylbenzene.

Substances which are advantageously used are mineral oils with a boilingrange of 170 to 220° C., white spirit with a boiling range of 170 to220° C., spindle oil with a boiling range of 250 to 350° C., petroleumor aromatics of boiling range 160 to 280° C., essence of terpentine andthe like.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boilingrange of 180 to 210° C. or high-boiling mixtures of aromatic andaliphatic hydrocarbons with a boiling range of 180 to 220° C. and/orspindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-type solvents of low volatility having anevaporation number of above 35 and a flashpoint of above 30° C.,preferably above 45° C., can be partially replaced by organochemicalsolvents of high or medium volatility, with the proviso that the solventmixture also has an evaporation number of above 35 and a flashpoint ofabove 30° C., preferably above 45° C., and that theinsecticide/fungicide mixture is soluble or emulsifiable in this solventmixture.

In a preferred embodiment, part of the organochemical solvent or solventmixture is replaced by an aliphatic polar organochemical solvent orsolvent mixture. Substances which are preferably used are aliphaticorganochemical solvents having hydroxyl and/or ester and/or ethergroups, such as, for example, glycol ethers, esters and the like.

The organochemical binders used within the scope of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se and can be diluted with water and/or are soluble ordispersible or emulsifiable in the organochemical solvents employed, inparticular binders composed of, or comprising, an acrylate resin, avinyl resin, for example polyvinyl acetate, polyester resin,polycondensation or polyaddition resin, polyurethane resin, alkyd resinor modified alkyd resin, phenol resin, hydrocarbon resin, such asindene/coumarone resin, silicone resin, drying vegetable and/or dryingoils and/or physically drying binders based on a natural and/orsynthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Up to 10% of bitumen or bituminoussubstances can also be used as binders. In addition, colorants,pigments, water repellents, odour-masking substances and inhibitors oranticorrosives known per se and the like can also be employed.

The composition or the concentrate preferably comprises, in accordancewith the invention, at least one alkyd resin or modified alkyd resinand/or a drying vegetable oil as the organochemical binder. Preferablyused according to the invention are alkyd resins with an oil content ofover 45% by weight, preferably 50 to 68% by weight.

All or some of the abovementioned binder can be replaced by a fixative(mixture) or a plasticizer (mixture). These additives are intended toprevent volatilization of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of binder employed).

The plasticizers are from the chemical classes of the phthalic esters,such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate,the phosphoric esters, such as tributyl phosphate, the adipic esters,such as di-(2-ethylhexyl) adipate, the stearates, such as butyl stearateor amyl stearate, the oleates, such as butyl oleate, the glycerol ethersor relatively high-molecular-weight glycol ethers, glycerol esters andp-toluenesulphonic esters.

Fixatives are chemically based on polyvinyl alkyl ethers, such as, forexample, polyvinyl methyl ether, or ketones, such as benzophenone orethylenebenzophenone.

Particularly suitable as a solvent or diluent is also water, ifappropriate as a mixture with one or more of the abovementionedorganochemical solvents or diluents, emulsifiers and dispersants.

Particularly effective protection of wood is achieved by large-scaleindustrial impregnation processes, for example vacuum, double-vacuum orpressure processes.

If appropriate, the ready-to-use compositions can additionally compriseother insecticides and, if appropriate, additionally one or morefungicides.

Suitable additional components which may be admixed are, preferably, theinsecticides and fungicides mentioned in WO 94/29 268. The compoundsmentioned in that document are expressly part of the presentapplication.

Very particularly preferred components which may be admixed areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxid,triflumuron, chlothianidin, spinosad, tefluthrin,

and fungicides, such as epoxyconazole, hexaconazole, azaconazole,propiconazole, tebuconazole, cyproconazole, metconazole, imazalil,dichlofluanid, tolylfluanid, 3-iodo-2-propinylbutyl carbamate,N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with salt wateror brackish water, in particular hulls, screens, nets, buildings,moorings and signalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the compounds according to theinvention, alone or in combination with other active compounds, have anoutstanding antifouling action.

Using the compounds according to the invention, alone or in combinationwith other active compounds, allows the use of heavy metals such as, forexample, in bis-(trialkyltin) sulphides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl-(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylenebisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thio-cyanate,copper naphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combination with the antifoulingcompositions according to the invention are:

algicides such as2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,dichlorophen, diuron, endothal, fentin acetate, isoproturon,methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;fungicides such asbenzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,tolylfluanid and azoles such as azaconazole, cyproconazole,epoxyconazole, hexaconazole, metconazole, propiconazole andtebuconazole;molluscicides such asfentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb andtrimethacarb; Fe chelates;or conventional antifouling active compounds such as4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl, potassium,copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,pyridine-triphenylborane, tetrabutyldistannoxane,2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide and2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as rosin to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds according to the invention are also suitable forcontrolling animal pests, in particular insects, arachnids and mites,which are found in enclosed spaces such as, for example, dwellings,factory halls, offices, vehicle cabins and the like. They can beemployed in domestic insecticide products for controlling these pestsalone or in combination with other active compounds and auxiliaries.They are active against sensitive and resistant species and against alldevelopment stages. These pests include:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus,Dermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae, Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus, Porcellioscaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus,Polydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina, Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalis,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotennes spp.,Reticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp.,Liposcelis spp.

From the order of the Coloptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxyscalcitrans, Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella, Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp., Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis, Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus, Triatoma infestans.

They are used in the household insecticides sector alone or incombination with other suitable active compounds such as phosphoricesters, carbamates, pyrethroids, growth regulators or active compoundsfrom other known classes of insecticides.

They are used in aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

The active compounds according to the invention can also be used asdefoliants, desiccants, haulm killers and, in particular, as weedkillers. Weeds in the broadest sense are understood as meaning allplants which grow at locations where they are undesired. Whether thesubstances according to the invention act as nonselective or selectiveherbicides depends essentially on the application rate.

The active compounds according to the invention can be used for examplein the following plants:

Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia,Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus,Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium,Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus,Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha,Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum,Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola,Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea,Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola,Xanthium.

Dicotyledonous crops of the genera: Arachis, Beta, Brassica, Cucumis,Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca,Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.

Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis,Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina,Cynodon, Cyperus, Dactyl-octenium, Digitaria, Echinochloa, Eleocharis,Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera,Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum,Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria,Sorghum.

Monocotyledonous crops of the genera: Allium, Ananas, Asparagus, Avena,Hordeum, Coryza, Panicum, Saccharum, Secale, Sorghum, Triticale,Triticum, Zea.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but extends in the same manner toother plants.

Depending on the concentration, the active compounds according to theinvention are suitable for the nonselective weed control on, forexample, industrial terrains and railway tracks and on paths andlocations with and without trees. Likewise the active compoundsaccording to the invention can be employed for controlling weeds inperennial crops, for example forests, ornamental tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hop fields, onlawns, turf and pastureland, and for the selective control of weeds inannual crops.

The compounds of the formula (I) according to the invention have strongherbicidal activity and a broad activity spectrum when used on the soiland on aerial plant parts. To a certain extent, they are also suitablefor the selective control of monocotyledonous and dicotyledonous weedsin monocotyledonous and dicotyledonous crops, both pre- andpost-emergence.

At certain concentrations or application rates, the active compoundsaccording to the invention can also be employed for controlling animalpests and fungal or bacterial plant diseases. If appropriate, they canalso be used as intermediates or precursors for the synthesis of otheractive compounds.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspoemulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants and/or foam-formers.

If the extender used is water, it is also possible to use, for example,organic solvents as auxiliary solvents. Suitable liquid solvents areessentially: aromatics, such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics and chlorinated aliphatic hydrocarbons, such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols, such as butanol orglycol, and also their ethers and esters, ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, stronglypolar solvents, such as dimethylformamide and dimethyl sulfoxide, andalso water.

Suitable solid carriers are: for example ammonium salts and groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, ground syntheticminerals, such as finely divided silica, alumina and silicates, suitablesolid carriers for granules are: for example crushed and fractionatednatural rocks such as calcite, marble, pumice, sepiolite and dolomite,and also synthetic granules of inorganic and organic meals, and granulesof organic material such as sawdust, coconut shells, maize cobs andtobacco stalks; suitable emulsifiers and/or foam-formers are: forexample non-ionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates andprotein hydrolysates; suitable dispersants are: for example lignosulfitewaste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, and also naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 percent by weightof active compounds, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in theirformulations, can also be used for weed control purposes as a mixturewith known herbicides and/or with substances which improve crop planttolerance (“safeners”), ready mixes or tank mixes being possible.Mixtures with herbicide products which contain one or more knownherbicides and a safener are hence also possible.

Herbicides which are suitable for the mixtures are known herbicides, forexample

acetochlor, acifluorfen(-sodium), aclonifen, alachlor,alloxydim(-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron,anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid,benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone,benzfendizone, benzobicyclon, benzofenap, benzoylprop (-ethyl),bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim,bromoxynil, butachlor, butafenacil(allyl), butroxydim, butylate,cafenstrole, caloxydim, carbetamide, carfentrazone(ethyl),chlomethoxyfen, chloramben, chloridazon, chlorimuron (-ethyl),chlornitrofen, chlorsulfuron, chlortoluron, cinidon(-ethyl),cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam (-methyl), cumyluron, cyanazine, cybutryne,cycloate, cyclosulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D,2,4-DB, desmedipham, diallate, dicamba, dichlorprop (—P), diclofop(-methyl), diclosulam, diethatyl (ethyl), difenzoquat, diflufeńican,diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn,dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr,diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin,ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron,etobenzanid, fenoxaprop (—P-ethyl), fentrazamide, flamprop (-isopropyl,-isopropyl-L, -methyl), flazasulfuron, florasulam, fluazifop (—P-butyl),fluazolate, flucarbazone (-sodium), flufenacet, flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron,fluoro-chloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil,flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone,fluoroxypyr (-butoxypropyl, -meptyl), flurprimidol, flurtamone,fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron, glufosinate(-ammonium), glyphosate (-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl, —P-methyl), hexazinone, imazamethabenz (-methyl),imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr,imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin,isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole,isoxapyrifop, lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet,mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron,metobromuron, (alpha-) metolachlor, metosulam, metoxuron, metribuzin,metsulfuron (-methyl), molinate, monolinuron, naproanilide, napropamide,neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl,oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat,pelargonic acid, pendimethalin, pendralin, pentoxazone, phenmedipham,picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron(-methyl), profluazol, prometryn, propachlor, propanil, propaquizafop,propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb,prosulfuron, pyraflufen (-ethyl), pyrazogyl, pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol,pyriftalide, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac,quinmerac, quinoclamine, quizalofop (—P-ethyl, —P-tefuryl), rimsulfuron,sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim,terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr,thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarbazil,tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr,tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl),tritosulfuron.

Others which are suitable for mixtures are known safeners, for example:

AD-67, BAS-145138, benoxacor, cloquintocet (-mexyl), cyometrinil, 2,4-D,DKA-24, dichlormid, dymron, fenclorim, fenchlorazol (-ethyl), flurazole,fluxofenim, furilazole, isoxadifen (-ethyl), MCPA, mecoprop (—P),mefenpyr (-diethyl), MG-191, oxabetrinil, PPG-1292, R-29148.

A mixture with other known active compounds, such as fungicides,insectides, acaricides, nematicides, bird repellents, plant nutrientsand soil conditioners, is also possible.

The active compounds can be applied as such, in the form of theirformulations or the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are applied in the customary manner, for example bypouring, spraying, atomizing, spreading.

The active compounds according to the invention can be applied bothbefore and after plant emergence. They can also be incorporated into thesoil prior to planting.

The application rate of active compound can vary within a substantialrange. Essentially, it depends on the nature of the desired effect. Ingeneral, the application rates are between 1 g and 10 kg of activecompound per hectare of soil area, preferably between 5 g and 5 kg perha.

The preparation and the use of the active compounds according to theinvention can be seen from the examples which follow.

PREPARATION EXAMPLES Process A Example I-1-a-1

6.7 g of the compound of Preparation Example II-1 in 40 ml of anhydroustoluene are added dropwise to 5.43 g (0.047 mol) of potassiumtert-butoxide in 18 ml of anhydrous tetrahydrofuran at refluxtemperature.

The reaction mixture is stirred under reflux for 1.5 h. Then, 60 ml ofwater are added, the aqueous phase is separated off and the organicphase is extracted with water. The aqueous phases are washed once morewith toluene and brought to pH 1 with concentrated hydrochloric acid at0-20° C. The precipitate is filtered off with suction, washed and dried.Purification is by column chromatography on silica gel(dichloromethane:ethyl acetate, 5:1).

Yield: 3.2 g/52% of theory). M.p.: >220° C.

Process P Example No. I-1-a-18

At 0° C. to 5° C., add 3.54 g of potassium tert-butoxide (95%) to 12.12g of iso-butanol; heat briefly. Then add the copper(I) iodide (0.571 g;3 mmol) and 1.34 g of the compound of Example I-a-10 (DE-A-10301804);then heat at 110° C. The mixture is stirred for 24 hours at 100° C. to110° C. The mixture is filtered with suction over Celite, the solids arediscarded and the filtrate is acidified and evaporated on a rotaryevaporator.

A separation by flash column chromatography on silica gel is carriedout, using ethyl acetate. The fractions which, according to LC/MS,contained the product were subjected to RP column chromatography with agradient programme. The column was preconditioned with a 50:50 mixtureof water and methanol.

Yield: 190 mg of white powder=15% of theory.

M.p.=117° C.

The following compounds of the formula (I-1-a) are obtained analogouslyto Example (I-1-a-1) and in accordance with the general preparationinstructions

(I-1-a)

Ex. No. W X Y D A B M.p. ° C. Isomer I-1-a-2 OCH₃ CH₃ Cl H—(CH₂)₂O—(CH₂)₂— >220 — I-1-a-3 OCH₃ C₂H₅ Cl H —(CH₂₂CHOCH₃—(CH₂)₂— 223 β I-1-a-4 OCH₃ C₂H₅ Cl H —(CH₂₂CHCH₃—(CH₂)₂—  232 β I-1-a-5 OCH₃C₂H₅ Cl H CH₃ CH₃  141 — I-1-a-6 OCH₃ C₂H₅ Cl H —(CH₂)₅—  236 — I-1-a-7OCH₃ C₂H₅ Cl

H  169 Isomer mixture I-1-a-8 OCH₃ CH₃ Cl H —(CH₂₂CHOCH₃—(CH₂)₂—  318 βI-1-a-9 OC₂H₅ C₂H₅ Cl H —(CH₂₂CHOCH₃—(CH₂)₂—  96 β I-1-a-10 OCH₃ CH₃ ClH CH₃ CH₃  266 — I-1-a-11 OC₂H₅ C₂H₅ Cl H CH₃ CH₃  207 — I-1-a-12 OCH₃C₂H₅ Cl C₂H₅ CH₃ H 176-178 — I-1-a-13 OCH₃ C₂H₅ Cl c-C₆H₁₁ CH₃ H  184 —I-1-a-14 OCH₃ C₂H₅ Cl

H H 154-157 — I-1-a-15 OCH₃ C₂H₅ Cl CH₃ C₂H₅ H *¹⁾ — I-1-a-16 OCH₃ C₂H₅Cl —(CH₂)₃— H Decomp. — I-1-a-17 OC₂H₅ C₂H₅ Cl H —(CH₂₂CHOCH₃—(CH₂)₂— 202 β I-1-a-18¹⁾ O—i-C₄H₉ C₂H₅ Cl H —(CH₂₂CHOCH₃—(CH₂)₂—  117 βI-1-a-19¹⁾

C₂H₅ Cl H —(CH₂₂CHOCH₃—(CH₂)₂— Wax*²⁾ β I-1-a-20¹⁾ O—CH₂—CH₂—OCH₃ C₂H₅Cl H —(CH₂₂CHOCH₃—(CH₂)₂—  61 β I-1-a-21¹⁾ OC₃H₇ C₂H₅ Cl H—(CH₂₂CHOCH₃—(CH₂)₂— Wax*³⁾ β *¹⁾¹H-NMR (400 MHz, d₆-DMSO): δ = 2.43(m, 2-H, Ar—CH₂—CH₃), 2.77 (s, 3H, N—CH₃) ppm *²⁾¹H-NMR (400 MHz,d₆-DMSO): δ = 2.43 (m, 2-H, Ar—CH ₂—CH₃), 3.82 (m, 2H, O—CH ₂CH₂) ppm*³⁾¹H-NMR (400 MHz, d₆-DMSO): δ = 0.27-0.3, 0.42-0.45 (2m, 4H,cyclopropyl-CH ₂), 1.02 (t, 3H, Ar CH₂—CH ₃) ppm ¹⁾Process P

Example No. I-1-b-1

200 mg (0.57 mol) of the compound of Example I-1-a-5 are introduced into5 ml of anhydrous ethyl acetate and treated with 0.94 ml (0.57 mmol) oftriethylamine. 0.71 ml (0.57 mmol) of isobutyryl chloride in 1 ml ofethyl acetate are added under reflux and the mixture is heated for 2.5 hunder reflux.

The reaction solution is cooled and concentrated and the residue ischromatographed on silica gel with a heptane/ethyl acetate gradient offrom 100/0 to 0/100.

Yield: 90 mg (43% of theory) M.p. 131° C.

The following compounds of the formula (I-1-b) are obtained analogouslyto Example (I-1-b-1) and following the general preparation instructions

(I-1-b)

Ex. No. W X Y D A B R¹ M.p. ° C. Isomer I-1-b-2 OCH₃ C₂H₅ Cl H —(CH₂)₅—i-C₃H₇ 221 — I-1-b-3 OCH₃ C₂H₅ Cl H —(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ 161 βI-1-b-4 OCH₃ C₂H₅ Cl H —(CH₂)₂—CHCH₃—(CH₂)₂— t-C₄H₉ 169 β I-1-b-5 OCH₃C₂H₅ Cl H CH₃ CH₃ t-C₄H₉ 148 — I-1-b-6 OCH₃ C₂H₅ Cl H—(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇ 201 β I-1-b-7 OC₂H₅ C₂H₅ Cl H CH₃ CH₃H₃C—O—CH₂ 130 — I-1-b-8 OCH₃ CH₃ Cl H CH₃ CH₃ H₃C—O—CH₂ 149-153 —I-1-b-9 OCH₃ C₂H₅ Cl

H H t-C₄H₉— *1.07 (s, 9H, t-Bu)— 2.40 (m, 2H, CH₂—Ar) — I-1-b-10 OCH₃C₂H₅ Cl CH₃ C₂H₅ H t-C₄H₉— Oil — I-1-b-11 OC₂H₅ C₂H₅ Cl H—(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇— 226-229 β I-1-b-12 OCH₃ C₂H₅ Cl H—(CH₂)₂—CHOCH₃—(CH₂)₂—

138 β I-1-b-13 OC₂H₅ C₂H₅ Cl H —(CH₂)₂—CHOCH₃—(CH₂)₂—

171 β I-1-b-14 OCH₃ C₂H₅ Cl H —(CH₂)₂—CHOCH₃—(CH₂)₂— C₂H₅—C(CH₃)₂—216-218 β I-1-b-15 OC₂H₅ C₂H₅ Cl H —(CH₂)₂—CHOCH₃—(CH₂)₂— C₂H₅—C(CH₃)₂—237-239 β I-1-b-16 OCH₃ C₂H₅ Cl II —(CH₂)₂—CHOCH₃—(CH₂)₂— H₅C₂—O—CH₂154-159 β I-1-b-17 OCH₃ C₂H₅ Cl H —(CH₂)₂—CHOCH₃—(CH₂)₂—(C₈H₁₇—CH═CH—C₇H₁₄— *3.21 (m, 1H, CHOCH₃) β 5.35 (m, 2H, CH═CH) *¹H-NMR(400 MHz, CDCl₃) : shifts δ in ppm

Example No. I-1-c-1

200 mg (0.57 mmol) of the compound of Example I-1-a-5 are introducedinto 5 ml of anhydrous CH₂Cl₂ and treated with 0.94 ml (0.57 mmol) oftriethylamine. 0.64 ml (0.57 mmol) of ethyl chloroformate in 1 ml ofCH₂Cl₂ are added at 10 to 20° C. and the mixture is stirred for 1.5 h atroom temperature. The reaction solution was concentrated and the residuewas chromatographed on silica gel with a heptane/ethyl acetate gradientof from 100/0 to 0/100.

Yield: 0.19 g (95% of theory) M.p. 222° C.

The following compounds of the formula (I-1-c) are obtained analogouslyto Example (I-1-c-1) and following the general preparation instructions

(I-1-c)

Ex. No. W X Y D A B M R² M.p. ° C. Isomer I-1-c-2 OCH₃ C₂H₅ Cl H—(CH₂)₅— O C₂H₅ 208 — I-1-c-3 OCH₃ C₂H₅ Cl H —(CH₂)₂—CHCH₃—(CH₂)₂— OC₂H₅ 187 β I-1-c-4 OCH₃ C₂H₅ Cl H —(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅ 161 βI-1-c-5 OCH₃ C₂H₅ Cl CH₃ C₂H₅ H O C₂H₅ *2.98 (s, 3H, NCH ₃)— — 3.71 (s,3H, OCH ₃) I-1-c-6 OCH₃ C₂H₅ Cl c-C₆H₁₁ CH₃ H O C₂H₅ *4.2 (m, 2H, OCH ₂)— I-1-c-7 OCH₃ C₂H₅ Cl C₂H₅ CH₃ H O C₂H₅ *4.2 (m, 2H, OCH ₂) I-1-c-8OCH₃ C₂H₅ Cl

H H O C₂H₅

— I-1-c-9 OCH₃ CH₃ Cl H CH₃ CH₃ O C₂H₅ 141-145 — I-1-c-10 OC₂H₅ C₂H₅ ClH CH₃ CH₃ O C₂H₅ *1.46 (d, 6H, — C(CH₃)₂) I-1-c-11 OC₂H₅ C₂H₅ Cl H—(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅ 188-191 β I-1-c-12 OC₂H₅ C₂H₅ Cl H—(CH₂)₂—CHOCH₃—(CH₂)₂— O CH₂═CH—CH₂— 159-161 β I-1-c-13 OCH₃ C₂H₅ Cl H—(CH₂)₂—CHOCH₃—(CH₂)₂— O CH₂═CH—CH₂— 138-140 β I-1-c-14 OCH₃ CH₃ Cl H—(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅ 170 β I-1-c-15 OCH₃ C₂H₅ Cl H—(CH₂)₂—CHOCH₃—(CH₂)₂— O

 98-101 β I-1-c-16 OC₂H₅ C₂H₅ Cl H —(CH₂)₂—CHOCH₃—(CH₂)₂— O

114 β I-1-c-17 OCH₃ C₂H₅ Cl —(CH₂)₃ — H O C₂H₅ *4.2 (m, 2H, OCH ₂)— —*¹H-NMR (400 MHz, CDCl₃) : shifts δ in ppm

Example I-d-1

First, 0.09 ml of triethylamine and then 0.069 g (0.601 mmol) ofmethanesulphonyl chloride are added to a solution of 0.2 g (0.547 mmol)of the compound of Example I-1-a-3 in anhydrous CH₂Cl₂. After themixture has been stirred overnight at room temperature, it is treatedwith 10 ml of sodium hydrogen carbonate solution, the phases areseparated and the organic phase is subsequently dried with sodiumsulphate and then freed from solvent in vacuo. The residue thus obtainedis chromatographed on silica gel with an n-heptane/ethyl acetategradient of from 100/0 to 0/100.

Yield: 0.14 g (58% of theory) M.p.: 210-214° C.

Example I-1-f-1

9 ml of a 10% strength solution of tetrahexylammonium hydroxide inmethanol are added to a solution of 0.75 g of the compound of ExampleI-1-a-3 (1.95 mmol) in 20 ml of anhydrous methanol and stirring iscontinued for 30 minutes at room temperature. The mixture is freed invacuo from solvent and treated with a total of three more portions of 50ml of methanol and the solvent is removed, which gives 1.44 g (yield97%) in the form of a waxy solid.

¹H NMR (400 MHz, d₆-DMSO): δ=0.88 (t, 12, 4 CH ₃), 3.56 (s, 3H, OCH ₃)ppm In Example I-1-f-2,

is obtained analogously to Example I-1-f-1.

¹H NMR (400 MHz, d₆-DMSO): δ=0.88 (t, 12, 4 CH ₃), 3.83 (s, 2H, OCH ₂)ppm

Example No. II-1

5.2 g of 4-chloro-2-methoxy-6-methylphenylacetic acid and 5.4 ml (0.073mol) of thionyl chloride are stirred at 50° C. until the evolution ofgas has ceased.

Excess thionyl chloride is evaporated on a rotary evaporator at 50° C.,the residue is taken up in 50 ml of anhydrous toluene, and excessthionyl chloride is again evaporated on a rotary evaporator. The residueis taken up in 30 ml of anhydrous tetrahydrofuran (solution 1). 5.1 g ofmethyl 1-amino-4-methylcyclohexanecarboxylate hydrochloride areintroduced into 50 ml of anhydrous tetrahydrofuran, and 7.5 ml (0.053mol) of triethylamine are added. Then, solution 1 is added dropwise at0-10° C.

Stirring is continued for 1 h at room temperature.

The solvent is evaporated on a rotary evaporator, the residue is takenup in a 0.5 N solution of hydrochloric acid in dichloromethane, themixture is extracted, the extract is dried and the solvent is distilledoff. The residue is recrystallized from MTB ether/n-hexane.

Yield: 6.7 g (68% of theory), m.p.: 166° C.

Example No. II-2

6.4 g of the compound of Preparation Example No. XXIX-1 in 60 ml ofmethylene chloride are added to 9.8 g (0.1 mol) of concentratedsulphuric acid at an internal temperature of 30-40° C. The mixture isstirred for 2 h at 30-40° C. Then, 13.5 ml of anhydrous methanol areadded in such a way that an internal temperature of 40° C. isestablished. Stirring is continued for 6 h at 40-70° C.

The reaction solution is poured onto 0.1 kg of ice, extracted withdichloromethane and washed with NaHCO₃ solution. The mixture is thendried, the solvent is distilled off and the residue is recrystallizedfrom MTB ether/n-hexane.

Yield: 5.9 g (83% of theory), m.p.: 156° C.

The following compounds of the formula II are obtained analogously toExamples II-1 and II-2 and following the general preparationinstructions

(II)

Ex. No. W X Y D A B R⁸ Isomer M.p. ° C. II-3 OCH₃ C₂H₅ Cl H—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β 105 II-4 OCH₃ C₂H₅ Cl H—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ β 131 II-5 OCH₃ C₂H₅ Cl H CH₃ CH₃ CH₃ — 163II-6 OCH₃ C₂H₅ Cl H —(CH₂)₅— CH₃ — 124 II-7 OCH₃ C₂H₅ Cl

H C₂H₅ Isomer mixture Oil II-8 OCH₃ C₂H₅ Cl H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃β 127 II-9 OC₂H₅ C₂H₅ Cl H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β 100 II-10 OCH₃C₂H₅ Cl H CH₃ CH₃ CH₃ — 157 II-11 OC₂H₅ C₂H₅ Cl H CH₃ CH₃ CH₃ — 118II-12 OCH₃ C₂H₅ Cl C₂H₅ CH₃ CH₃ CH₃ — *1.47 (d, 3H, CH(CH ₃)) II-13 OCH₃C₂H₅ Cl c-C₆H₁₁ CH₃ H C₂H₅ — *1.44 (d, 3H, CH(CH ₃)) II-14 OCH₃ C₂H₅ Cl

H H C₂H₅ —

II-15 OCH₃ C₂H₅ Cl CH₃ C₂H₅ H C₂H₅ — *2.59 (q, 2H, Ar—CH ₂) II-16 OCH₃C₂H₅ Cl —(CH₂)₃— H CH₃ — **1.13 (t, 3H, ArCH₂—CH ₃), 3.76 (s, 3H, Ar OCH₃) 11-17 OC₂H₅ CH₃ Cl H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β ***1.31 (t, 3H,Ar—O—CH₂—CH ₃), 4.00 (q, 2H, Ar—O—CH ₂—CH₃) *¹H NMR (400 MHz, CDCl₃):shifts δ in ppm **¹H NMR (400 MHz, d₆-DMSO): shifts δ in ppm ***¹H NMR(400 MHz, CD₃CN): shifts δ in ppm

Example No. XXIX-1

5.2 g of 4-chloro-2-methoxy-6-methylphenylacetic acid and 5.4 ml (0.073mol) of thionyl chloride are stirred at 50° C. until the evolution ofgas has ceased.

Excess thionyl chloride is evaporated on a rotary evaporator at 50° C.,the residue is taken up in 50 ml of anhydrous toluene and excess thionylchloride is again evaporated on a rotary evaporator. The residue istaken up in 30 ml of anhydrous tetrahydrofuran (solution 1). 6.11 g of4-aminotetrahydropyran-4-carbonitrile are introduced into 50 ml ofanhydrous tetrahydrofuran, 3.4 ml of triethylamine are added andsolution 1 is added dropwise at 0-10° C.

Stirring is continued for 1 h at room temperature.

The solvent is evaporated on a rotary evaporator and the residue istaken up in a 0.5 N strength solution of hydrochloric acid indichloromethane, the mixture is extracted, the extract is dried and thesolvent is distilled off. The residue is recrystallized from MTBether/n-hexane.

Yield: 6.4 g (82% of theory), m.p.: 149° C.

Example I-2-a-1

4.2 g of the compound of Example III-1, dissolved in DMF (5 ml), areadded dropwise at 0 to 10° C. to 1.84 g of KOtBu in 5 ml of DMF at 0° C.The mixture is stirred overnight at room temperature and the DMF isremoved by vacuum distillation. The residue is stirred with water,acidified with HCl, and the precipitate is filtered off with suction anddried.

Yield: 2.8 g (59% of theory), m.p. 90° C.

The following compounds of the formula (I-2-a) are obtained analogouslyto Example (I-2-a-1) and following the general preparation instructions

(I-2-a)

Ex. No. W X Y A B M.p. ° C. I-2-a-2 OCH₃ C₂H₅ Cl —(CH₂)₂—CHOCH₃—(CH₂)₂—90-95

Example I-2-b-1

0.34 g of the compound of Example I-2-a-1 are introduced intodichloromethane (10 ml) and triethylamine (0.15 ml), and 0.13 g ofpivaloyl chloride is added, with ice-cooling. The mixture is stirredovernight at room temperature and the solution is washed with 10% citricacid and 10% NaOH, separated, dried and concentrated.

Yield 0.3 g (57% of theory).

¹H-NMR (400 MHz, CD₃CN): δ=1.11 (s, 9H, C(CH ₃)₃), 3.72 (s, 3H, ArOCH ₃)ppm.

The following compounds of the formula (I-2-b) are obtained analogouslyto Example (I-2-b-1) and following the general preparation instructions

(I-2-b)

Ex. No. W X Y A B R¹ M.p. ° C. I-2-b-2 OCH₃ C₂H₅ Cl —(CH₂)₅—H₅C₂—C(CH₃)₂

I-2-b-3 OCH₃ C₂H₅ Cl —(CH₂)₅— i-C₃H₇ *2.66 (m, 1H, —CH(CH₃)₂, 3.72 (s,3H, OCH₃ I-2-b-4 OCH₃ C₂H₅ Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— H₅C₂—C(CH₃)₂—*3.28, 3.33 (2s, 3H, CH—OCH ₃) I-2-b-5 OCH₃ C₂H₅ Cl—(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇ *3.30, 3.32 (2s, 3H, CH—OCH ₃) I-2-b-6OCH₃ C₂H₅ Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉ *3.29, 3.33 (2s, 3H, CHOCH₃), 1.11, 1.12 (2s, 9H, C(CH ₃)₃) *¹H NMR (400 MHz, CD₃CN): shifts δ inppm

Example I-2-c-1

0.67 g of the compound of Example I-2-a-1 are introduced intodichloromethane (10 ml) and triethylamine (0.31 ml), and 0.239 g ofethyl chloroformate is added, with ice-cooling. The mixture is stirredovernight at room temperature and the solution is washed with 10% citricacid and 10% NaOH, separated, dried and concentrated.

Yield: 0.76 g (73% of theory).

¹H NMR (400 MHz, CD₃CN): δ=3.73 (s, 3H, OCH₃), 4.03 (q, 2H, OCH ₂CH₃),6.87 (d, 1H, Ar—H), 6.95 (d, 1H, Ar—H) ppm.

The following compounds of formula (I-2-c) are obtained analogously toExample (I-2-c-1) and following the general preparation instructions

(I-2-c)

Ex. No. W X Y A B M R² M.p. ° C. I-2-c-2 OCH₃ C₂H₅ Cl—(CH₂)—CHOCH₃—(CH₂)₂— O C₂H₅ *3.31, 3.33 (2s, 3H, CHOCH₃), 3.73 (s, 3H,OCH₃ *¹H NMR (400 MHz, CDCN): shifts δ in ppm

Example III-1

2.09 g of ethyl 1-hydroxycyclohexanecarboxylate and 3 g of the compoundof Example XXIV-1 are heated at 120° C. in an oil bath, stirred untilthe evolution of gas has ceased and then heated briefly at 140° C.Yield: 42 g (59% of theory).

¹H NMR (400 MHz, CD₃CN): δ=2.58 (q, 2H, CH ₂—Ar), 3.77 (s, 3H, OCH₃),4.05 (m, 2H, O—CH ₂—CH₃) ppm.

The following compounds of formula (III) are obtained analogously toExample III-1 and following the general preparation instructions

(III)

Ex. No. W X Y A B R⁸ M.p. ° C. III-2 OCH₃ C₂H₅ Cl —(CH₂)₂CHOCH₃—(CH₂)₂—C₂H₅ *2.58 (q, 2H, CH ₂—Ar), 4.06 (m, 2H, O—CH ₂—CH₃), 6.88 (d, 1H,Ar—H), 6.91 (d, 1H, Ar—H)

Example I-8-a-1

2.5 g (0.007 mol) of the compound of Example XII-1 and 1.673 g (0.015mol) of potassium tert-butoxide are heated in 100 ml ofN,N-dimethylacetamide to 60 to 120° C. The mixture is cooled, acidified,diluted with water and extracted 3 times with toluene. The organic phaseis dried, the solvent is removed by vacuum distillation and the residueis filtered through silica gel. This gives 0.9 g of product.

The aqueous phase was reextracted with ethyl acetate and the extract waspurified analogously. This gave a further 0.48 g of product.

Total yield: 1.38 g (60% of theory), m.p. 163° C.

Example I-8-b-1

0.14 g of the compound of Example I-8-a-1 and 0.08 ml of triethylamineare introduced into 25 ml of dichloromethane. After 0.05 ml ofisobutyryl chloride has been added dropwise, the mixture is stirred for1 hour at room temperature and then diluted with water, the organicphase is separated off and the solvent is distilled off. The reactionmixture is stirred with n-hexane and a little toluene, and theprecipitate is filtered off with suction.

Yield: 120 mg (70% of theory), m.p.: 127.5° C.

Example I-8-c-1

0.15 g of the compound of Example I-8-a-1 and 0.08 ml of triethylamineare introduced into 35 ml of dichloromethane, 0.04 ml of ethylchloroformate is added dropwise and the mixture is stirred for 1 hour atroom temperature. The reaction solution is diluted with water, theorganic phase is separated off and dried and the solvent is distilledoff. The residue is stirred with n-hexane and a little toluene and theprecipitate is filtered off with suction.

Yield: 110 mg (60% of theory), m.p.: 110° C.

Example XII-1

1.9 g of the compound of Example XXVII-2 in 50 ml of dichloromethane aretreated with 2.10 g of oxalyl dichloride, the mixture is refluxed for 30minutes, 1 ml of dimethylformamide is added, the mixture is stirred fora further 30 minutes under reflux, cooled under N₂ atmosphere, thesolvent is distilled off and the residue is dissolved in acetonitrile(solution A).

1.31 g of the compound of Example XLI-2 and 1.38 g of potassiumcarbonate are introduced into 100 ml of acetonitrile, solution A isadded dropwise at room temperature and stirring is continued for 4 hoursat room temperature. The solids are filtered off, the solvent isevaporated and the residue is filtered through silica gel.

Yield: 2.5 g (83% of theory).

¹H NMR (400 MHz, CDCl₃): δ=6.85 (d, 1H); 6.70 (d, 1H); 4.50 (ddbr, 1H);4.30-4.10 (m, 3H); 3.90 (d, 1H); 3.75 (s, 3H); 3.50 (d, 1H); 2.70 (mbr,2H); 2.60 (q, 2H); 1.65 (mbr, 4H); 1.30 (tr, 3H); 1.20 (tr, 3H) ppm.

Example XLI-1

5 g (0.031 mol) of hexahydropyridazine are introduced into 35 ml ofdichloromethane, the mixture is treated with 32 ml of water and 0.1 g oftetra-n-butylammonium bromide is added. 4.1 g (0.104 mmol) of sodiumhydroxide in 32 ml of water are metered in, while cooling in an icebath. 3.0 ml of ethyl chloroformate in 30 ml of dichloromethane areadded dropwise at 0° C. and the mixture is stirred for 2 hours at 0° C.After the mixture has been stirred for 8 hours at room temperature, theorganic phase is separated off, the aqueous phase is extracted withdichloromethane and the organic phase is concentrated by evaporation ona rotary evaporator. The reaction mixture is stirred with water,acidified slightly and washed twice with diethyl ether, and the aqueousphase is basified, extracted with dichloromethane, dried andconcentrated by evaporation on a rotary evaporator.

Yield: 3.1 g (63% of theory)

¹H NMR (400 MHz, CDCl₃): δ=4.20 (q, 2H); 3.55 (tr, br, 2H); 2.90 (tr,br, 2H); 1.65 (m, 4H); 1.30 (tr, 3H) ppm.

Example XXIV-1

5.78 g of the compound of Example XXVII-2 are introduced into 50 ml oftoluene and one drop of DMF. 3.6 g of thionyl chloride are addeddropwise at room temperature, and the mixture is stirred overnight underreflux, cooled, concentrated and degassed.

Yield: 6.17 g (98% of theory).

The product was used without further purification, for example for thepreparation of Examples III-1 and III-2.

Ex. No. XXVII-1

34 g (0.11 mol) of the compound of Preparation Example XLII-1 areintroduced, at room temperature, into 350 ml of tert-butanol and 115 gof 2-methyl-2-butene. A solution of 456 ml of water, 155.9 g of NaH₂PO₄and 53.9 g of sodium chlorite as a 20% strength solution is then addeddropwise at room temperature. Continue stirring for 4 h at roomtemperature.

The reaction solution is stirred into ethyl acetate, and the organicphase is separated off and extracted twice with ethyl acetate. It issubsequently dried and the solvent is distilled off. The residue istaken up in water, rendered alkaline and extracted. The aqueous phase isacidified and the precipitate is filtered off with suction and dried.

Yield: 11.2 g (47.5% of theory), m.p.: 130-135° C.

Example No. XLII-1

22 g (0.11 mol) of the compound of Preparation Example XLIII-1 isintroduced into 60 ml of CH₂Cl₂ at −70° C. Then, ozone is passed in for2 hours until uptake is no longer discernible (KI solution turnsyellowish-brown). The mixture is flushed with oxygen. When the reactionhas ended, 19.4 g of dimethyl sulphide are added dropwise at −70° C.using a pipette, and stirring is continued for 30 minutes. The mixtureis allowed to slowly come to room temperature and stirring is continuedfor 30 minutes at room temperature. The solvent is evaporated in vacuoon a rotary evaporator in a hood.

The residue is now purified by chromatography on silica gel (petroleumether:ethyl acetate, 15:1).

Yield: 34 g (40% of theory).

Example No. XLIII-1

28 g (0.15 mol) of 3-chloro-6-allyl-5-methylphenol of Example B togetherwith 7.4 g (0.18 mol) of NaOH are introduced into 70 ml of H₂O. 20.4 g(0.165 mol) of dimethyl sulphate are added dropwise at 20-30° C. andstirring is continued for 7 h at 100° C. The aqueous phase is extracted3 times with diethyl ether and the organic phase is washed twice with 1NNaOH solution and water. It is dried, the solvent is evaporated on arotary evaporator and the residue is distilled in vacuo.

Yield: 22 g (b.p.: 65° C.; 0.2 mbar, 76% of theory).

Example A

50 g (0.35 mol) of 3-chloro-5-methylphenol, 46.7 g (0.38 mol) ofbrompropene and 50 g of potassium carbonate are introduced into 80 ml ofanhydrous acetone at room temperature. The mixture is refluxedovernight.

The reaction mixture is cooled, treated with 150 ml of water andextracted twice with methyl tert-butyl ether. The organic phase issubsequently washed with 10% strength NaOH solution and dried overpotassium carbonate. The solvent is evaporated on a rotary evaporatorand the residue is distilled in vacuo.

Yield: 54 g (b.p.: 105° C. at 0.1 mbar; 85% of theory)

Example B

To 53 g (0.29 mol) of the compound of Preparation Example A, add 150 mlof mesitylene at room temperature and reflux for 1-2 days. After thereaction has ended (TLC check), the solvent is evaporated in vacuo on arotary evaporator. Precision distillation of 110 g of crude product invacuo gives two isomers, which are introduced into the subsequentreaction for the preparation of Ex. XLIII-1 without furtherpurification.

Yield: 28 g (b.p.: 84° C.; 0.12 mbar, 53% of theory) (crude product).

Example No. XXXI-1

30.1 g (103 mmol) of methyl 2-bromo-4-chloro-6-ethylphenylacetate, 3 g(21 mmol) of copper(I) bromide, 30 ml of ethyl acetate and 210 ml (1105mmol) of 30% strength sodium methoxide solution are refluxed overnight.The solvent is subsequently evaporated on a rotary evaporator, theresidue is taken up in water/dichloromethane, the mixture is extracted,the extract is dried and the solvent is evaporated on a rotaryevaporator.

Yield: 9.4 g (38% of theory)

¹H NMR {400 MHz, DMSO-d₆}: 1.09 (t, ³J_(HH)=7 Hz, 3H, CH₃); 2.55 (q,³J_(HH)=7 Hz, 2H, CH₂); 3.58 (s, 3H, OCH₃); 3.61 (s, 2H, CH₂) 3.78 (s,3H, OCH₂); 6.89 (s, 1H, Ph-H); 6.94 (s, 1H, Ph-H).

MS/CI: 243 (M+1)

Ethyl 2-ethyl-6-ethoxy-4-chlorophenylacetate (XXX-2) is obtainedanalogously to Example XXX-1

¹H NMR {400 MHz, DMSO-d₆}: 1.10 (t, ³J_(HH)=7 Hz, 3H, CH₃); 1.18 (t,³J_(HH)=7 Hz, 3H, CH₃); 1.27 (t, ³J_(HH)=7 Hz, 3H, CH₃); 2.54 (q,³J_(HH)=7 Hz, 2H, CH₂); 3.58 (s, 2H, CH₂); 4.01 (q, ³J_(HH)=7 Hz, 2H,OCH₂) 4.09 (q, ³J_(HH)=7 Hz, 2H, OCH₂); 6.86 (s, 1H, Ph-H); 6.88 (s, 1H,Ph-H) ppm.

MS/CI 271 (M+1).

Example No. XXVII-2

9.4 g (38 mmol) of the compound of Example XXXI-1 are added to 6.5 g(116 mmol) of KOH, 30 ml of water and 40 ml of methanol and the mixtureis refluxed overnight. The solvent is then removed in vacuo, and theresidue is taken up in water and precipitated with concentrated HCl. Theprecipitate is filtered, washed with a little water and dried in vacuo.

Yield: 8.6 g (97% of theory)

¹H NMR {400 MHz, DMSO-d₆}: 1.08 (t, ³J_(HH)=7 Hz, 3H, CH₃); 2.53 (q,³J_(HH)=7 Hz, 2H, CH₂); 3.51 (s, 3H, CH₂); 3.76 (s, 3H, OCH₃); 6.86 (s,1H, Ph-H); 6.89 (s, 1H, Ph-H); 12.2 (s, 1H, CO₂H).

MS/CI: 229 (M+1)

2-Ethyl-6-ethoxy-4-chlorophenylacetic acid XXXVII-3 is obtainedanalogously to Example XXVII-2

¹H NMR {400 MHz, DMSO-d₆}: 1.09 (t, ³J_(HH)=7 Hz, 3H, CH₃); 1.28 (t,³J_(HH)=7 Hz, 3H, CH₃); 2.54 (q, ³J_(HH)=7 Hz, 2H, CH₂); 3.51 (s, 2H,CH₂); 4.01 (q, ³J_(HH)=7 Hz, 2H₂OCH₂); 6.85 (s, 1H, Ph-H); 6.87 (s, 1H,Ph-H); 12.2 (s 1H, CO₂H) ppm.

MS/CI-243 (M+1).

Use Examples Example A Post-Emergence Test

Solvent: 5 parts by weight of acetoneEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active compound preparation, 1 part by weight ofactive compound is mixed with the stated amount of solvent, the statedamount of emulsifier is added, and the concentrate is diluted with waterto the desired concentration.

Test plants with a height of 5-15 cm are sprayed with the activecompound preparation in such a way that the amounts of active compounddesired in each case are applied per unit area. The concentration of thespray mixture is chosen in such a way that the amounts of activecompound desired in each case are applied in 1 000 1 of water/ha.

After three weeks, the degree of damage of the plants is scored in %damage in comparison with the development of the untreated control.

The figures denote:

-   -   0%=no effect (like untreated control)    -   100%=total destruction

Example B Pre-Emergence Test

Solvent: 5 parts by weight of acetoneEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active compound preparation, 1 part by weight ofactive compound is mixed with the stated amount of solvent, the statedamount of emulsifier is added, and the concentrate is diluted with waterto the desired concentration.

Seeds of the test plant are sown in normal soil. After approximately 24hours, the soil is sprayed with the active compound preparation in sucha way that the amounts of active compound desired in each case areapplied per unit area. The concentration of the spray mixture is chosenin such a way that the amounts of active compound desired in each caseare applied in 1 000 1 of water/ha.

After three weeks, the degree of damage of the plants is scored in %damage in comparison with the development of the untreated control.

The figures denote:

-   -   0%=no effect (like untreated control)    -   100%=total destruction

post-emergence greenhouse g a.i./ha sugar beet Alopecurus Avena fatuaEchinochloa Setaria Abutilon Sinapis Ex. I-1-a-3 250 0 100 100 100 10070 80 post-emergence greenhouse g a.i./ha sugar beet Alopecurus Avenafatua Echinochloa Setaria Ex. I-1-a-4 250 0 100 100 100 100post-emergence greenhouse g a.i./ha Alopecurus Avena fatua EchinochloaSetaria Sinapis Ex. I-1-a-5 250 100 100 100 100 80 Ex. I-1-a-6 250 90100 100 — 80 post-emergence greenhouse g a.i./ha sugar beet AlopecurusAvena fatua Setaria Amaranthus Ex. I-1-a-1 250 0 100 100 100 — Ex.I-1-a-2 250 0 — 100 100 90 pre-emergence greenhouse g a.i./ha AlopecurusAvena fatua Echinochloa Setaria Abutilon Sinapis Ex. I-1-a-3 250 80 100100 100 80 80 Ex. I-1-a-4 250 90 100 100 100 — 90 pre-emergencegreenhouse g a.i./ha Alopecurus Avena fatua Echinochloa Setaria Ex.I-1-a-5 250 90 100 100 100 pre-emergence greenhouse g a.i./ha sugar beetAlopecurus Lolium Setaria Cassia Matricaria Viola Ex. I-1-a-1 125 0 100100 100 100 90 90 pre-emergence greenhouse g a.i./ha sugar beetAlopecurus Avena fatua Setaria Ex. I-1-a-2 250 0 100 80 80

Example C Post-Emergence Crop Plant Tolerance

Seeds of monocotyledonous and dicotyledonous weed and crop plants areplaced in sandy loam in wood fibre pots or in plastic pots, covered withsoil and grown in the greenhouse or, during the vegetation period, inthe open outside the greenhouse, under good growth conditions. 2 to 3weeks after sowing, the test plants are treated in the one- tothree-leaf stage. The test compounds, which are formulated as wettablepowder (WP) or as a fluid (EC), are sprayed onto the plants and the soilsurface at various dosage rates with a water application rate of 300l/ha (converted), with added wetter (0.2 to 0.3%). 3 to 4 weeks afterthe treatment of the test plants, the effect of the preparations isscored visually in comparison with untreated controls (herbicidalactivity in percent (%): 100% activity=plants have died, 0%activity=like control plants).

Use of Safeners

If it is additionally desired to test whether safeners are capable ofimproving the plant tolerance of test substances with regard to the cropplants, the following options for applying the safeners are used:

-   -   Prior to application of the test substances, the crop plants are        sprayed with safener at a particular application rate per        hectare (usually 1 day prior to application of the test        substances).    -   The safener is applied together with the test substance in the        form of a tank mix (the amount of safener being indicated in        g/ha or as a safener:herbicide ratio).

The activity of the safener substance can be assessed in comparison withuntreated control plants by comparing the effect of test substances oncrop plants which have been treated without and with safener.

Results of Greenhouse Experiments with Safener/Pretreatment (SafenerMefenpyr (100 g a.i./ha), One Day Prior to Post-Emergence Treatment withthe Herbicide)

TABLE 1′ Application rate Spring barley g a.i./ha observed (%) ExampleI-1-c-7 50 85 25 30 13 15 Example I-1-c-7 + 500 + 100  50 mefenpyr 25 +100 10 13 + 100 5

TABLE 2′ Application rate Spring barley Spring wheat g a.i./ha observed(%) observed (%) Example I-1-c-8 100  55 50 97 50 25 35 ExampleI-1-c-8 + 100 + 100  20 mefenpyr 50 + 100 50 15 25 + 100 15

TABLE 3′ Application rate Spring barley Spring wheat g a.i./ha observed(%) observed (%) Example I-2-a-1 100  20 30 50 15 20 25 10 20 ExampleI-2-a-1 + 100 + 100  10 15 mefenpyr 50 + 100 0 10 25 + 100 0 5

TABLE 4′ Application rate Spring barley g a.i./ha observed (%) ExampleI-2-a-2 100 97 50 60 25 60 Example I-2-a-2 + 100 + 100  40 mefenpyr 50 +100 30 25 + 100 20

TABLE 5′ Application rate Spring wheat g a.i./ha observed (%) ExampleI-2-c-1 100  30 50 20 Example I-2-c-1 + 100 + 100  10 mefenpyr 50 + 1005

TABLE 6′ Application rate Spring barley Spring wheat g a.i./ha observed(%) observed (%) Example I-2-b-1 100  20 60 50 10 40 25 20 ExampleI-2-b-1 + 100 + 100  10 15 mefenpyr 50 + 100 0 10 25 + 100 5

TABLE 7′ Application rate Spring barley g a.i./ha observed (%) ExampleI-2-b-6 100 98 50 97 25 50 Example I-2-b-6 + 100 + 100  20 mefenpyr 50 +100 15 25 + 100 10

TABLE 8′ Application rate Spring wheat g a.i./ha observed (%) ExampleI-1-c-1 100  70 50 20 25 20 Example + 100 + 100  55 mefenpyr 50 + 100 525 + 100 5

TABLE 9′ Application rate Spring barley Spring wheat g a.i./ha observed(%) observed (%) Example I-2-b-4 100  80 100 25 Example I-2-b-4 + 100 +100  20 20 mefenpyr 25 + 100

TABLE 10′ Application rate Spring barley Spring wheat g a.i./ha observed(%) observed (%) Example I-2-b-5 100  100 50 97 25 50 99 ExampleI-2-b-5 + 100 + 100  30 mefenpyr 50 + 100 20 25 + 100 10 20Greenhouse Experiment with Cereals with 100 g a.i./ha Mefenpyr,Post-Emergence; Evaluation 21 Days after Application

TABLE 11′ Application rate Winter Winter g a.i./ha barley (%) wheat (%)Example I-1-a-6 50 20 10 Example I-1-a-6 + 50 + 100 0 3 mefenpyrContainer Experiments with Cereals Outside the GreenhouseHerbicide: mefenpyr 1:2 Tank Mix

TABLE F′-1 Application rate Spring barley Spring wheat g a.i./haobserved (%) observed (%) Example I-2-a-2 50 20 95 Example I-2-a-2 +50 + 100 5 15 mefenpyr

TABLE F′-2 Application rate Spring barley Spring wheat g a.i./haobserved (%) observed (%) Example I-2-c-1 100 15 40 Example I-2-c-1 +100 + 200 0 5 mefenpyr

TABLE F′-3 Application rate Spring barley Spring wheat g a.i./haobserved (%) observed (%) Example I-2-c-2 100 100 100 Example I-2-c-2 +100 + 200 15 70 mefenpyr

TABLE F′-4 Application rate Spring barley Spring wheat g a.i./haobserved (%) observed (%) Example I-2-b-1 100 20 30 Example I-2-b-1 +100 + 200 0 0 mefenpyr

TABLE F′-5 Application rate Spring barley Spring wheat g a.i./haobserved (%) observed (%) Example I-2-b-6 50 40 100 Example I-2-b-6 +50 + 100 10 15 mefenpyr

TABLE F′-6 Application rate Spring barley Spring wheat g a.i./haobserved (%) observed (%) Example I-1-c-1 100 98 98 Example I-1-c-1 +100 + 200 20 65 mefenpyr

TABLE F′-7 Application rate Spring barley g a.i./ha observed (%) ExampleI-1-b-4 50 60 Example I-1-b-4 + 50 + 100 15 mefenpyr

Container Experiments with Cereals Outside the Greenhouse

Herbicide: mefenpyr g: 50 g a.i./ha

TABLE F′-8 Application rate Spring barley g a.i./ha observed (%) ExampleI-2-c-2 100 98 Example I-2-c-2 + 100 + 50 25 mefenpyr

TABLE F′-9 Application rate Spring barley Spring wheat g a.i./haobserved (%) observed (%) Example I-2-c-1 100 50 65 Example I-2-c-1 +100 + 50 5 5 mefenpyr

Example D Aphis Test, Contact Action

Solvent: 7 parts by weight of dimethylformamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active compound preparation, 1 part by weight ofactive compound is mixed with the stated amounts of solvent andemulsifier and the concentrate is diluted with water to the desiredconcentration.

Shoots of young field bean plants (Vicia faba) which are severelyinfested with black bean aphids (Aphis fabae) are treated by beingdipped into the active compound preparation of the desiredconcentration.

After the desired period of time, the destruction is determined in %.100% means that all of the aphids have been destroyed; 0% means that noaphids have been destroyed.

In this test, for example the following compounds of the PreparationExamples show a good activity:

TABLE D Plant-injurious insects Aphis fabae contact test Active compoundDestruction Active compounds concentration in ppm in % after 6 d Ex.I-1-a-1 1000 100

Example E Meloidogyne Test

Solvent: 7 parts by weight of dimethylformamideEmulsifier 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active compound preparation, I part by weight ofactive compound is mixed with the stated amounts of solvent andemulsifier and the concentrate is diluted with water to the desiredconcentration.

Containers are filled with sand, active compound solution, Meloidogyneincognita egg/larval suspension and lettuce seeds. The lettuce seedsgerminate and the plantlets develop. The galls develop on the roots.

After the desired time, the nematicidal efficacy is determined I n %with reference to gall formation. 100% means that no galls were found;0% means that the number of galls on the treated plants corresponds tothat of the untreated control.

In this test, good activity is shown, for example, by the followingcompounds of the Preparation Examples:

TABLE E Plant-injurious nematodes Meloidogyne test Active compoundDestruction Active compounds concentration in ppm in % after 14 d Ex.I-1-a-3 20 98 Ex. I-1-a-4 20 98

Example F Myzus Test

Solvent: 7 parts by weight of dimethylformamideEmulsifier 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active compound preparation, 1 part by weight ofactive compound is mixed with the stated amounts of solvent andemulsifier and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea), which are severely infested with thegreen peach aphid (Myzus persicae) are treated by immersing them intothe active compound preparation of the desired concentration.

After the desired time, the destruction rate is determined in %. 100%means that all of the aphids have been destroyed; 0% means that none ofthe aphids have been destroyed.

In this test, good activity is shown, for example, by the followingcompounds of the Preparation Examples:

TABLE F Plant-injurious insects Myzus test Active compound DestructionActive compounds concentration in ppm in % after 6 d Ex. I-1-a-1 1000 95Ex. I-1-a-2 1000 100 Ex. I-1-a-3 1000 90

Example G Nephotettix Test

Solvent: 7 parts by weight of dimethylformamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Rice seedlings (Oryza sativa) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with the green rice leafhopper (Nephotettix cincticeps) whilethe leaves are still moist.

After the desired time, the destruction in % is determined. 100% meansthat all the leafhoppers have been killed; 0% means that none of theleafhoppers have been killed.

In this test, for example the following compounds of the preparationexamples show good effectiveness:

TABLE G Plant-injurious insects Nephotettix test Active compoundDestruction Active compounds concentration in ppm in % after 6 d Ex.I-1-a-1 1000 100 Ex. I-1-a-2 1000 100

Example H Phaedon Larvae Test

Solvent: 7 parts by weight of dimethylformamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with the larvae of the mustard beetle (Phaedon cochleariae)while the leaves are still moist.

After the desired time, the destruction in % is determined. 100% meansthat all the beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, for example the following compounds of the preparationexamples show good effectiveness:

TABLE H Plant-injurious insects Phaedon larvae test Active compoundDestruction Active compounds concentration in ppm in % after 7 d Ex.I-1-a-1 1000 100 Ex. I-1-a-2 1000 100 Ex. I-1-a-3 1000 80 Ex. I-1-a-41000 100 Ex. I-1-a-6 1000 90

Example I Plutella Test

Solvent: 7 parts by weight of dimethylformamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with caterpillars of the diamond-back moth (Plutellaxylostella) while the leaves are still moist.

After the desired time, the destruction in % is determined. 100% meansthat all the caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, for example the following compounds of the preparationexamples show good effectiveness:

TABLE I Plant-injurious insects Plutella test Active compoundDestruction Active compounds concentration in ppm in % after 7 d Ex.I-1-a-1 1000 100 Ex. I-1-a-2 1000 100

Example J Spodoptera frugiperda Test

Solvent: 7 parts by weight of dimethylformamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with caterpillars of the armyworm (Spodoptera frugiperda) whilethe leaves are still moist.

After the desired time, the destruction in % is determined. 100% meansthat all the caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, for example the following compounds of the preparationexamples show good effectiveness:

TABLE J Plant-injurious insects Spodoptera frugiperda test Activecompound Destruction Active compounds concentration in ppm in % after 7d Ex. I-1-a-1 1000 100

Example K Tetranychus Test (OP-Resistant/Immersion Treatment)

Solvent: 7 parts by weight of dimethylformamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Bean plants (Phaseolus vulgaris) which are severely infested with allstages of the greenhouse red spider mite (Tetranychus urticae) aredipped into a preparation of the active compound of the desiredconcentration.

After the desired time, the activity in % is determined. 100% means thatall the spider mites have been killed; 0% means that none of the spidermites have been killed.

In this test, for example the following compounds of the preparationexamples show good effectiveness:

TABLE K Plant-injurious mites Tetranychus test (OP-resistant/immersiontreatment) Active compound Destruction Active compounds concentration inppm in % after 7 d Ex. I-1-a-1 1000 100 Ex. I-1-a-2 1000 95 Ex. I-1-a-3100 80

Example L Limit Concentration Test/Soil-Dwelling Insects—Treatment ofTransgenic Plants

Test insect: Diabrotica balteata—larvae in the soilSolvent: 7 parts by weight of acetoneEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added, and the concentrate is dilutedwith water to the desired concentration.

The active compound preparation is poured on the soil. The concentrationof the active compound in the preparation is of virtually no importance,only the amount of weight of active compound per unit volume of soil,which is detailed in ppm (mg/l), being decisive. 0.25 l pots are filledwith the soil and left to stand at 20° C.

Immediately after setting up the experiment, 5 pregerminated maizekernels cv. YIELD GUARD (trade mark of Monsanto Comp., USA) are placedinto each pot. After 2 days, the test insects in question are placedinto the treated soil. After a further 7 days, the efficacy of theactive compound is determined by counting the maize plants which haveemerged (1 plant=20% activity).

Example M Heliothis virescens Test—Treatment of Transgenic Plants

Solvent: 7 parts by weight of acetoneEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

Soybean shoots (Glycine max) cv. Roundup Ready (trade mark of MonsantoComp. USA) are treated by dipping them into the active compoundpreparation of the desired concentration and are populated withcaterpillars of the tobacco budworm (Heliothis virescens) while theleaves are still moist.

After the desired time, the destruction of the insects is determined.

1-35. (canceled)
 36. A compound of formula (I)

in which W represents alkoxy, halogenoalkoxy, alkoxyalkyloxy,alkoxy-bis-alkyloxy, or optionally substitutedcycloalkylalkanediyloxythat is optionally interrupted by hetero atoms, Xrepresents alkyl, Y represents chlorine, bromine, or iodine, and CKErepresents a group

in which A represents hydrogen; represents alkyl, alkenyl, alkoxyalkyl,or alkylthioalkyl, each of which is optionally substituted by halogen;represents saturated or unsaturated, optionally substituted cycloalkylin which one or more ring atoms are optionally replaced by a heteroatom; or represents aryl, arylalkyl, or hetaryl, each of which isoptionally substituted by halogen, alkyl, halogenoalkyl, alkoxy,halogenoalkoxy, cyano, or nitro, D represents hydrogen; represents anoptionally substituted radical selected from the series consisting ofalkyl, alkenyl, alkynyl, alkoxyalkyl, and saturated or unsaturatedcycloalkyl in which one or more ring members are optionally replaced byhetero atoms; or represents arylalkyl, aryl, hetarylalkyl, or hetaryl,or A and D together with the atoms to which they are bonded represent asaturated or unsaturated cycle that is unsubstituted or substituted inthe A,D moiety and optionally contains one or more hetero atoms, and Grepresents hydrogen (a) or a group

in which E represents a metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur, M represents oxygen or sulphur, R¹represents alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, orpoly-alkoxyalkyl, each of which is optionally substituted by halogen;represents cycloalkyl that is optionally interrupted by one or morehetero atoms and is optionally substituted by halogen, alkyl, or alkoxy;or represents optionally substituted phenyl, phenylalkyl, hetaryl,phenoxyalkyl, or hetaryloxyalkyl, R² represents alkyl, alkenyl,alkoxyalkyl, or polyalkoxyalkyl, each of which is optionally substitutedby halogen; or represents optionally substituted cycloalkyl, phenyl, orbenzyl, R³, R⁴ and R⁵ independently of one another represent alkyl,alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, orcycloalkylthio, each of which is optionally substituted by halogen; orrepresent optionally substituted phenyl, benzyl, phenoxy, or phenylthio,and R⁶ and R⁷ independently of one another represent hydrogen; representalkyl, cycloalkyl, alkenyl, alkoxy, or alkoxyalkyl, each of which isoptionally substituted by halogen; represent optionally substitutedphenyl; or represent optionally substituted benzyl; or R⁶ and R⁷together with the N atom to which they are bonded represent a cycle thatis optionally interrupted by oxygen or sulphur.
 37. A compound offormula (I) according to claim 36 in which W represents C₁-C₆-alkoxy,C₁-C₆-halogenoalkoxy, C₁-C₄-alkoxy-C₂-C₄-alkyloxy,C₁-C₄-alkoxy-bis-C₂-C₄-alkyloxy, or representsC₃-C₆-cycloalkyl-C₁-C₃-alkanediyloxythat is optionally monosubstitutedto trisubstituted by fluorine, chlorine, C₁-C₃-alkyl, or C₁-C₃-alkoxyand in which one methylene group of the ring is optionally interruptedby oxygen or sulphur, X represents C₁-C₆-alkyl, Y represents chlorine,bromine, or iodine, and CKE represents a group

in which A represents hydrogen; represents C₁-C₁₂-alkyl, C₃-C₈-alkenyl,C₁-C₁₀-alkoxy-C₁-C₈-alkyl, or C₁-C₁₀-alkylthio-C₁-C₆-alkyl, each ofwhich is optionally substituted by halogen; represents C₃-C₈-cycloalkylin which one or two ring members that are not directly adjacent areoptionally replaced by oxygen and/or sulphur and that is optionallysubstituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy; or representsphenyl, naphthyl, hetaryl having 5 to 6 ring atoms, phenyl-C₁-C₆-alkyl,or naphthyl-C₁-C₆-alkyl, each of which is optionally substituted byhalogen, C₁-C₆-alkyl, C₁-C₆-halogenoalkyl, C₁-C₆-alkoxy,C₁-C₆-halogenoalkoxy, cyano, or nitro, D represents hydrogen; representsC₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl, orC₁-C₁₀-alkoxy-C₂-C₈-alkyl, each of which is optionally substituted byhalogen; represents C₃-C₈-cycloalkyl in which a ring member isoptionally replaced by oxygen or sulphur and that is optionallysubstituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, orC₁-C₄-halogenoalkyl; or represents phenyl, hetaryl having 5 or 6 ringatoms, phenyl-C₁-C₆-alkyl, or hetaryl-C₁-C₆-alkyl having 5 or 6 ringatoms, each of which is optionally substituted by halogen, C₁-C₆-alkyl,C₁-C₆-halogenoalkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkoxy, cyano, ornitro, or A and D together represent optionally substitutedC₃-C₆-alkanediyl or C₃-C₆-alkenediyl, in which one methylene group isoptionally replaced by a carbonyl group, oxygen, or sulphur, whereinsuitable substituents for A and D together are halogen, hydroxyl, ormercapto, or are C₁-C₁₀-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio,C₃-C₇-cycloalkyl, phenyl, or benzyloxy, each of which is optionallysubstituted by halogen; or are a further C₃-C₆-alkanediyl,C₃-C₆-alkenediyl, or butadienyl group that is itself optionallysubstituted by C₁-C₆-alkyl or in which two adjacent substituentstogether with the carbon atoms to which they are bonded optionally forma further saturated or unsaturated cycle having 5 or 6 ring atoms thatoptionally contain oxygen or sulphur or that optionally contains a group

and G represents hydrogen (a) or a group

in which E represents a metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur, M represents oxygen or sulphur, R¹represents C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl,C₁-C₈-alkylthio-C₁-C₈-alkyl, or poly-C₁-C₈-alkoxy-C₁-C₈-alkyl, each ofwhich is optionally substituted by halogen; represents C₃-C₈-cycloalkylin which one or more ring members that are not directly adjacent areoptionally replaced by oxygen and/or sulphur and that is optionallysubstituted by halogen, C₁-C₆-alkyl, or C₁-C₆-alkoxy; represents phenylthat is optionally substituted by halogen, cyano, nitro, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl, C₁-C₆-halogenoalkoxy,C₁-C₆-alkylthio, or C₁-C₆-alkylsulphonyl; represents orphenyl-C₁-C₆-alkyl that is optionally substituted by halogen, nitro,cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl, orC₁-C₆-halogenoalkoxy; represents 5- or 6-membered hetaryl that isoptionally substituted by halogen or C₁-C₆-alkyl; representsphenoxy-C₁-C₆-alkyl that is optionally substituted by halogen orC₁-C₆-alkyl; or represents 5- or 6-membered hetaryloxy-C₁-C₆-alkyl thatis optionally substituted by halogen, amino or C₁-C₆-alkyl, R²represents C₁-C₂₀alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl, orpoly-C₁-C₈-alkoxy-C₂-C₈-alkyl, each of which is optionally substitutedby halogen; or represents C₃-C₈-cycloalkyl that is optionallysubstituted by halogen, C₁-C₆-alkyl, or C₁-C₆-alkoxy; or representsphenyl or benzyl, each of which is optionally substituted by halogen,cyano, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl, orC₁-C₆-halogenoalkoxy, R³ represents C₁-C₈-alkyl that is optionallysubstituted by halogen; or represents phenyl or benzyl, each of which isoptionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, cyano, or nitro, R⁴ and R⁵independently of one another represent C₁-C₈-alkyl, C₁-C₈-alkoxy,C₁-C₈-alkylamino, di(C₁-C₈-alkyl)amino, C₁-C₈-alkylthio,C₂-C₈-alkenylthio, or C₃-C₇-cycloalkylthio, each of which is optionallysubstituted by halogen; or represents phenyl, phenoxy, or phenylthio,each of which is optionally substituted by halogen, nitro, cyano,C₁-C₄-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-alkylthio,C₁-C₄-halogenoalkylthio, C₁-C₄-alkyl, or C₁-C₄-halogenoalkyl, R⁶ and R⁷independently of one another represent hydrogen; represent C₁-C₈-alkyl,C₃-C₈-cycloalkyl, C₁-C₈-alkoxy, C₃-C₈-alkenyl, orC₁-C₈-alkoxy-C₁-C₈-alkyl, each of which is optionally substituted byhalogen; represent phenyl that is optionally substituted by halogen,C₁-C₈-halogenoalkyl, C₁-C₈-alkyl, or C₁-C₈-alkoxy; or represent benzylthat is optionally substituted by halogen, C₁-C₈-alkyl,C₁-C₈-halogenoalkyl, or C₁-C₈-alkoxy; or R⁶ and R⁷ together represent aC₃-C₆-alkylene radical that is optionally substituted by C₁-C₄-alkyl andin which one carbon atom is optionally replaced by oxygen or sulphur,R¹³ represents hydrogen, C₁-C₈-alkyl or C₁-C₈-alkoxy, each of which isoptionally substituted by halogen, C₃-C₈-cycloalkyl in which onemethylene group is optionally replaced by oxygen or sulphur and which isoptionally substituted by halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy, orphenyl, phenyl-C₁-C₄-alkyl or phenyl-C₁-C₄-alkoxy, each of which isoptionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, nitro or cyano, R^(14a)represents hydrogen or C₁-C₈-alkyl, or R¹³ and R^(14a) togetherrepresent C₄-C₆-alkanediyl, R^(15a) and R^(16a) are identical ordifferent and represent C₁-C₆-alkyl, or R^(15a) and R^(16a) togetherrepresent a C₂-C₄-alkanediyl radical that is optionally substituted byC₁-C₆-alkyl, by C₁-C₆-halogenoalkyl, or by phenyl that is optionallysubstituted by halogen, C₁-C₆-alkyl, C₁-C₄-halogenoalkyl, C₁-C₆-alkoxy,C₁-C₄-halogenoalkoxy, nitro, or cyano, R^(17a) and R^(18a) independentlyof one another represent hydrogen; represent C₁-C₈-alkyl that isoptionally substituted by halogen; or represent phenyl that isoptionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, nitro or cyano, or R^(17a)and R^(18a) together with the carbon atom to which they are bondedrepresent a carbonyl group or C₅-C₇-cycloalkyl in which one methylenegroup is optionally replaced by oxygen or sulphur and that is optionallysubstituted by halogen, C₁-C₄-alkyl, or C₁-C₄-alkoxy, and R^(19a) andR^(20a) independently of one another represent C₁-C₁₀-alkyl,C₂-C₁₀-alkenyl, C₁-C₁₀-alkoxy, C₁-C₁₀-alkylamino, C₃-C₁₀-alkenylamino,di(C₁-C₁₀-alkyl)amino, or di(C₃-C₁₀-alkenyl)amino.
 38. A compound offormula (I) according to claim 36 in which W represents C₁-C₄-alkoxy,C₁-C₄-halogenoalkoxy, C₁-C₃-alkoxy-C₂-C₃-alkyloxy,C₁-C₂-alkoxy-bis-C₂-C₃-alkyloxy or C₃-C₆-cycloalkyl-C₁-C₂-alkanediyloxyin which one methylene group of the ring can optionally be interruptedby oxygen, X represents C₁-C₃-alkyl, Y represents chlorine or bromine,and CKE represents a group

in which A represents hydrogen; represents C₁-C₆-alkyl orC₁-C₄-alkoxy-C₁-C₂-alkyl, each of which is optionally monosubstituted totrisubstituted by fluorine or chlorine; represents C₃-C₆-cycloalkyl thatis optionally monosubstituted or disubstituted by C₁-C₂-alkyl, orC₁-C₂-alkoxy; or represents phenyl or benzyl, each of which isoptionally monosubstituted or disubstituted by fluorine, chlorine,bromine, C₁-C₄-alkyl, C₁-C₂-halogenoalkyl, C₁-C₄-alkoxy,C₁-C₂-halogenoalkoxy, cyano, or nitro, D represents hydrogen; representsC₁-C₆-alkyl, C₃-C₆-alkenyl, or C₁-C₄-alkoxy-C₂-C₃-alkyl, each of whichis optionally monosubstituted to trisubstituted by fluorine; representsC₃-C₆-cycloalkyl that is optionally monosubstituted or disubstituted byC₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl and in which onemethylene group is optionally replaced by oxygen; or when CKE is a groupother than group (1), represents phenyl or pyridyl, each of which isoptionally monosubstituted or disubstituted by fluorine, chlorine,bromine, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, orC₁-C₄-halogenoalkoxy, or A and D together represent C₃-C₅-alkanediylthat is optionally monosubstituted or disubstituted with C₁-C₂-alkyland/or C₁-C₂-alkoxy and in which one methylene group is optionallyreplaced by a carbonyl group except when CKE is group (1), oxygen orsulphur; and G represents hydrogen (a) or a group

in which E represents a metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur, M represents oxygen or sulphur, R¹represents C₁-C₈-alkyl, C₂-C₁₈-alkenyl, C₁-C₄-alkoxy-C₁-C₂-alkyl, orC₁-C₄-alkylthio-C₁-C₂-alkyl, each of which is optionally monosubstitutedto trisubstituted by fluorine or chlorine; represents C₃-C₆-cycloalkylthat is optionally monosubstituted or disubstituted by fluorine,chlorine, C₁-C₂-alkyl, or C₁-C₂-alkoxy and in which one or two ringmembers that are not directly adjacent are optionally replaced byoxygen; or represents phenyl that is optionally monosubstituted ordisubstituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl,C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl, or C₁-C₂-halogenoalkoxy, R²represents C₁-C₈-alkyl, C₂-C₈-alkenyl, or C₁-C₄-alkoxy-C₂-C₄-alkyl, eachof which is optionally monosubstituted to trisubstituted by fluorine;represents C₃-C₆-cycloalkyl that is optionally monosubstituted byC₁-C₂-alkyl or C₁-C₂-alkoxy; or represents phenyl or benzyl, each ofwhich is optionally monosubstituted or disubstituted by fluorine,chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, C₁-C₃-alkoxy,trifluoromethyl, or trifluoromethoxy, R³ represents C₁-C₆-alkyl that isoptionally monosubstituted to trisubstituted by fluorine; or representsphenyl that is optionally in each case monosubstituted by fluorine,chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, trifluoromethyl,trifluoromethoxy, cyano, or nitro, R⁴ represents C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₆-alkylamino, di(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio,C₃-C₄-alkenylthio, or C₃-C₆-cycloalkylthio; or represents phenyl,phenoxy, or phenylthio, each of which is optionally monosubstituted byfluorine, chlorine, bromine, nitro, cyano, C₁-C₃-alkoxy,C₁-C₃-halogenoalkoxy, C₁-C₃-alkylthio, C₁-C₃-halogenoalkylthio,C₁-C₃-alkyl, or trifluoromethyl, R⁵ represents C₁-C₆-alkoxy orC₁-C₆-alkylthio, R⁶ represents hydrogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl,C₁-C₆-alkoxy, C₃-C₆-alkenyl, or C₁-C₆-alkoxy-C₁-C₄-alkyl; representsphenyl that is optionally monosubstituted by fluorine, chlorine,bromine, trifluoromethyl, C₁-C₄-alkyl, or C₁-C₄-alkoxy; or representsbenzyl that is optionally monosubstituted by fluorine, chlorine,bromine, C₁-C₄-alkyl, trifluoromethyl, or C₁-C₄-alkoxy, and R⁷represents C₁-C₆-alkyl, C₃-C₆-alkenyl, or C₁-C₆-alkoxy-C₁-C₄-alkyl, orR⁶ and R⁷ together represent a C₄-C₅-alkylene radical that is optionallysubstituted by methyl or ethyl and in which one methylene group isoptionally replaced by oxygen or sulphur.
 39. A compound of formula (I)according to claim 36 in which W represents methoxy, ethoxy, n-propoxy,iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, methoxy-ethyloxy,ethoxy-ethyloxy, cyclopropyl-methoxy, cyclopentyl-methoxy, orcyclohexyl-methoxy, X represents methyl or ethyl, Y represents chlorineor bromine, and CKE represents a group

in which A represents hydrogen; represents C₁-C₄-alkyl orC₁-C₂-alkoxy-C₁-C₂-alkyl, each of which is monosubstituted totrisubstituted by fluorine; represents cyclopropyl, cyclopentyl, orcyclohexyl; or when CKE is a group other than group (5), representsphenyl that is optionally substituted by fluorine, chlorine, bromine,methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl,trifluoromethoxy, cyano, or nitro, D represents hydrogen; representsC₁-C₄-alkyl, C₃-C₄-alkenyl, or C₁-C₄-alkoxy-C₂-C₃-alkyl, each of whichis optionally monosubstituted to trisubstituted by fluorine; representscyclopropyl, cyclopentyl, or cyclohexyl; or when CKE is a group otherthan group (1), represents phenyl or pyridyl, each of which isoptionally monosubstituted by fluorine, chlorine, methyl, ethyl,n-propyl, iso-propyl, methoxy, ethoxy, or trifluoromethyl, or A and Dtogether represent C₃-C₅-alkanediyl that is optionally monosubstitutedby methyl or methoxy and in which one carbon atom is optionally replacedby oxygen or sulphur; and G represents hydrogen (a) or a group

 —SO₂—R³ (d), or E (f), in which L represents oxygen or sulphur, Mrepresents oxygen or sulphur, E represents an ammonium ion, R¹represents C₁-C₆-alkyl, C₂-C₁₇-alkenyl, C₁-C₂-alkoxy-C₁-alkyl, orC₁-C₂-alkylthio-C₁-alkyl; represents cyclopropyl or cyclohexyl, each ofwhich is optionally monosubstituted by fluorine, chlorine, methyl, ormethoxy; or represents phenyl that is optionally monosubstituted byfluorine, chlorine, bromine, cyano, nitro, methyl, methoxy,trifluoromethyl, or trifluoromethoxy, R² represents C₁-C₈-alkyl,C₂-C₆-alkenyl, or C₁-C₄-alkoxy-C₂-C₃-alkyl, phenyl, or benzyl, each ofwhich is optionally monosubstituted by fluorine, and R³ representsC₁-C₈-alkyl.
 40. A compound of formula (I) according to claim 36 inwhich W represents methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy,iso-butoxy, sec-butoxy, methoxy-ethyloxy, ethoxy-ethyloxy, orcyclopropylmethoxy, X represents methyl or ethyl, Y represents chlorine,CKE represents a group

in which A represents hydrogen, methyl, ethyl, cyclopropyl, isopropyl,n-propyl, isobutyl, n-butyl, t-butyl or s-butyl, D represents hydrogen,methyl, ethyl, isopropyl, cyclopropyl, or cyclohexyl, or A and Dtogether represent C₃-C₅-alkanediyl, and G represents hydrogen (a) or agroup

 —SO₂—R³ (d), or E (f), in which L represents oxygen, M representsoxygen, E represents an ammonium ion (N⁺(C₆H₁₃)₄), R¹ representsC₁-C₈-alkyl, C₁-C₂-alkoxy-C₁-alkyl, or C₂-C₁₇-alkenyl, R² representsC₁-C₈-alkyl or C₂-C₆-alkenyl, and R³ represents C₁-C₄-alkyl.
 41. Aprocess for the preparation of compounds of formula (I) according toclaim 36 comprising (A) for compounds of formula (I-8-a)

in which A, D, W, X, and Y have the meanings given for formula (I) inclaim 36, reacting a compound of formula (X)

in which A and D have the meanings given for formula (I) in claim 36,(α) with a compound of formula (VI)

in which X, Y, and W have the meanings given for formula (I) in claim36, Hal represents halogen, optionally in the presence of a diluent andoptionally in the presence of an acid acceptor, or (β) with a compoundof formula (XI)

in which W, X, and Y have the meanings given for formula (I) in claim36, U represents NH₂ or O—R⁸, and R⁸ represents alkyl, optionally in thepresence of a diluent and optionally in the presence of a base, or (γ)with a compound of formula (XII)

in which A, D, W, X, Y, and R⁸ have the meanings given for formula (XI),optionally in the presence of a diluent and optionally in the presenceof a base, or (B) for compounds of formula (I-8-b)

in which A, D, R¹, W, X, and Y have the meanings given for formula (I)in claim 36, reacting compounds of formula (I-8-a) shown above in whichA, D, W, X and Y have the meanings given for formula (I) in claim 36,(α) with an acid chloride of formula (XIII)

in which R¹ has the meanings given for formula (I) in claim 36, and Halrepresents halogen, or (β) with a carboxylic anhydride of formula (XIV)R¹—CO—O—CO—R¹  (XIV) in which R¹ has the meanings given for formula (I)in claim 36, optionally in the presence of a diluent and optionally inthe presence of an acid-binding agent; or (C) for compounds of formula(I-8-c)

in which A, D, R², M, W, X, and Y have the meanings given for formula(I) in claim 36, and L represents oxygen, reacting compounds of formulas(I-1-a) to (I-8-a) shown above in which A, D, W, X and Y have themeanings given for formula (I) in claim 36, with a chloroformic ester orchloroformic thioester of formula (XV)R²-M-CO—Cl  (XV) in which R² and M have the meanings given for formula(I) in claim 36, optionally in the presence of a diluent and optionallyin the presence of an acid-binding agent; or (D) for compounds offormula (I-8-c)

in which A, D, R², M, W, X, and Y have the meanings given for formula(I) in claim 36, and L represents sulphur, reacting compounds offormulas (I-1-a) to (I-8-a) shown above in which A, D, W, X and Y havethe meanings given for formula (I) in claim 36, with achloromonothioformic ester or chlorodithioformic ester of formula (XVI)

in which R² and M have the meanings given for formula (I) in claim 36,optionally in the presence of a diluent and optionally in the presenceof an acid-binding agent; or (E) for compounds of formula (I-8-d)

in which A, D, R³, W, X and Y have the meanings given for formula (I) inclaim 36, reacting compounds of formulas (I-1-a) to (I-8-a) shown abovein which A, D, W, X and Y have the meanings given for formula (I) inclaim 36, with a sulphonyl chloride of formula (XVII)R³—SO₂—Cl  (XVII) in which R³ has the meanings given for formula (I) inclaim 36, optionally in the presence of a diluent and optionally in thepresence of an acid-binding agent; or (F) for compounds of formula(I-8-e)

in which A, D, L, R⁴, R⁵, W, X, and Y have the meanings given forformula (I) in claim 36, reacting compounds of formulas (I-1-a) to(I-8-a) shown above in which A, D, W, X and Y have the meanings givenfor formula (I) in claim 36, with a phosphorus compound of formula(XVIII)

in which L, R⁴, and R⁵ have the meanings given for formula (I) in claim36, and Hal represents halogen, optionally in the presence of a diluentand optionally in the presence of an acid-binding agent, or (G) forcompounds of formula (I-8-f)

in which A, D, E, W, X and Y have the meanings given for formula (I) inclaim 36, reacting compounds of formulas (I-1-a) to (I-8-a) shown abovein which A, D, W, X and Y have the meanings given for formula (I) inclaim 36, (α) with a metal compound of formula (XIX)Me(OR¹⁰)_(t)  (XIX) in which Me represents a mono- or divalent metal,and t represents the number 1 or 2, optionally in the presence of adiluent, or (β) with an amine of formulae (XX)

in which R¹⁰, R¹¹ and R¹² independently of one another representhydrogen or alkyl, optionally in the presence of a diluent, or (H) forcompounds of formula (I-8-g)

in which A, D, L, R⁶, R⁷, W, X, and Y have the meanings given forformula (I) in claim 36, reacting compounds of formulas (I-1-a) to(I-8-a) shown above in which A, D, W, X and Y have the meanings givenfor formula (I) in claim 36, (α) with an isocyanate or isothiocyanate offormula (XXI)R⁶—N═C=L  (XXI) in which R⁶ and L have the meanings given for formula(I) in claim 36, optionally in the presence of a diluent and optionallyin the presence of a catalyst, or (β) with a carbamoyl chloride orthiocarbamoyl chloride of formula (XXII)

in which L, R⁶, and R⁷ have the meanings given for formula (I) in claim36, optionally in the presence of a diluent and optionally in thepresence of an acid-binding agent.
 42. A compound of formula (XXIV)

in which W represents alkoxy, halogenoalkoxy, alkoxyalkyloxy,alkoxy-bis-alkyloxy, or optionally substitutedcycloalkylalkanediyloxythat is optionally interrupted by hetero atoms, Xrepresents alkyl, Y represents chlorine, bromine, or iodine, and Zrepresents a leaving group introduced by a reagent for the activation ofcarboxylic acids.
 43. A compound of formula (XXVII)

in which W represents alkoxy, halogenoalkoxy, alkoxyalkyloxy,alkoxy-bis-alkyloxy, or optionally substitutedcycloalkylalkanediyloxythat is optionally interrupted by hetero atoms, Xrepresents alkyl, and Y represents chlorine, bromine, or iodine.
 44. Acompound of formula (XXXI)

in which W represents alkoxy, halogenoalkoxy, alkoxyalkyloxy,alkoxy-bis-alkyloxy, or optionally substitutedcycloalkylalkanediyloxythat is optionally interrupted by hetero atoms, Xrepresents alkyl, Y represents chlorine, bromine, or iodine, and R⁸represents alkyl.
 45. A composition with an effective content of anactive compound combination comprising the components, (a′) one or moresubstituted cyclic ketoenols of formula (I) according to claim 36, and(b′) one or more compounds that improves crop plant tolerance selectedfrom the group consisting of the compounds4-dichloroacetyl-1-oxa-4-aza-spiro[4.5]-decane (AD-67, MON-4660),1-dichloroacetyl-hexahydro-3,3,8a-trimethyl-pyrrolo[1,2-a]-pyrimidin-6(2H)-one(dicyclonon, BAS-145138),4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (benoxacor),1-methyl-hexyl 5-chloro-quinolin-8-oxy-acetate (cloquintocet-mexyl),3-(2-chloro-benzyl)-1-(1-methyl-1-phenyl-ethyl)-urea (cumyluron),α-(cyanomethoximino)-phenylacetonitrile (cyometrinil),2,4-dichloro-phenoxyacetic acid (2,4-D),4-(2,4-dichloro-phenoxy)-butyric acid (2,4-DB),1-(1-methyl-1-phenyl-ethyl)-3-(4-methyl-phenyl)-urea (daimuron, dymron),3,6-dichloro-2-methoxy-benzoic acid (dicamba), S-1-methyl-1-phenyl-ethylpiperidine-1-thiocarboxylate (dimepiperate),2,2-dichloro-N-(2-oxo-2-(2-propenylamino)-ethyl)-N-(2-propenyl)-acetamide(DKA-24), 2,2-dichloro-N,N-di-2-propenyl-acetamide (dichlormid),4,6-dichloro-2-phenyl-pyrimidine (fenclorim), ethyl1-(2,4-dichloro-phenyl)-5-trichloro-methyl-1H-1,2,4-triazole-3-carboxylate(fenchlorazole-ethyl), phenylmethyl2-chloro-4-trifluoromethyl-thiazole-5-carboxylate (flurazole),4-chloro-N-(1,3-dioxolan-2-yl-methoxy)-α-trifluoro-acetophenone oxime(fluxofenim), 3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyl-oxazolidine(furilazole, MON-13900), ethyl4,5-dihydro-5,5-diphenyl-3-isoxazolecarboxylate (isoxadifen-ethyl,1-(ethoxycarbonyl)-ethyl-3,6-dichloro-2-methoxybenzoate (lactidichlor),(4-chloro-o-tolyloxy)-acetic acid (MCPA),2-(4-chloro-o-tolyloxy)-propionic acid (mecoprop), diethyl1-(2,4-dichloro-phenyl)-4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylate(mefenpyr-diethyl), 2-dichloro-methyl-2-methyl-1,3-dioxolane (MG-191),2-propenyl-1-oxa-4-azaspiro[4.5]-decane 4-carbodithioate (MG-838),1,8-naphthalic anhydride,α-(1,3-dioxolan-2-yl-methoximino)-phenylacetonitrile (oxabetrinil),2,2-dichloro-N-(1,3-dioxolan-2-yl-methyl)-N-(2-propenyl)-acetamide(PPG-1292), 3-dichloroacetyl-2,2-dimethyl-oxazolidine (R-28725),3-dichloroacetyl-2,2,5-trimethyl-oxazolidine (R-29148),4-(4-chloro-o-tolyl)-butyric acid, 4-(4-chloro-phenoxy)-butyric acid,diphenylmethoxyacetic acid, methyl diphenylmethoxyacetate, ethyldiphenylmethoxyacetate, methyl1-(2-chloro-phenyl)-5-phenyl-1H-pyrazole-3-carboxylate, ethyl1-(2,4-dichloro-phenyl)-5-methyl-1H-pyrazole-3-carboxylate, ethyl1-(2,4-dichloro-phenyl)-5-isopropyl-1H-pyrazole-3-carboxylate, ethyl1-(2,4-dichloro-phenyl)-5-(1,1-dimethyl-ethyl)-1H-pyrazole-3-carboxylate,ethyl 1-(2,4-dichloro-phenyl)-5-phenyl-1H-pyrazole-3-carboxylate, ethyl5-(2,4-dichloro-benzyl)-2-isoxazoline-3-carboxylate, ethyl5-phenyl-2-isoxazoline-3-carboxylate, ethyl5-(4-fluoro-phenyl)-5-phenyl-2-isoxazoline-3-carboxylate,1,3-dimethyl-but-1-yl 5-chloro-quinolin-8-oxy-acetate, 4-allyloxy-butyl5-chloro-quinolin-8-oxy-acetate, 1-allyloxy-prop-2-yl5-chloro-quinolin-8-oxy-acetate, methyl 5-chloro-quinolin-8-oxy-acetate,ethyl 5-chloro-quinolin-8-oxy-acetate, allyl5-chloro-quinoxalin-8-oxy-acetate, 2-oxo-prop-1-yl5-chloro-quinolin-8-oxy-acetate, diethyl5-chloro-quinolin-8-oxy-malonate, diallyl5-chloro-quinoxalin-8-oxy-malonate, diethyl5-chloro-quinolin-8-oxy-malonate, 4-carboxy-chroman-4-yl-acetic acid(AC-304415), 4-chloro-phenoxy-acetic acid,3,3′-dimethyl-4-methoxy-benzo-phenone,1-bromo-4-chloromethylsulphonyl-benzene,1-[4-(N-2-methoxybenzoyl-sulphamoyl)-phenyl]-3-methyl-urea (aliasN-(2-methoxy-benzoyl)-4-[(methyl-aminocarbonyl)-amino]-benzenesulphonamide),1-[4-(N-2-methoxybenzoylsulphamoyl)-phenyl]-3,3-dimethyl-urea,1-[4-(N-4,5-dimethylbenzoylsulphamoyl)-phenyl]-3-methyl-urea,1-[4-(N-naphthylsulphamoyl)-phenyl]-3,3-dimethyl-urea,N-(2-methoxy-5-methyl-benzoyl)-4-(cyclopropylaminocarbonyl)-benzenesulphonamide,a compound of formula (IIa)

in which X¹ represents nitro, cyano, halogen, C₁-C₄-alkyl, C₁-C₄halogenoalkyl, C₁-C₄-alkoxy, or C₁-C₄-halogenoalkoxy; n represents anumber of between 0 and 5; A¹ represents a divalent heterocyclic groupof the formulas

R¹⁹ represents hydrogen, cyano, or halogen or represents C₁-C₄-alkyl,C₃-C₆-cycloalkyl or phenyl, each of which is optionally substituted byfluorine, chlorine, and/or bromine; R²⁰ represents hydrogen orrepresents C₁-C₆-alkyl, C₃-C₆-cycloalkyl, or tri(C₁-C₄-alkyl)silyl, eachof which is optionally substituted by hydroxyl, cyano, halogen, orC₁-C₄-alkoxy; R²¹ represents hydrogen, cyano, or halogen or representsC₁-C₄-alkyl, C₃-C₆-cycloalkyl, or phenyl, each of which is optionallysubstituted by fluorine, chlorine, and/or bromine; and R¹⁴ representshydroxyl, mercapto, amino, C₁-C₆-alkoxy, C₁-C₆-alkylthio,C₁-C₆-alkylamino, or di(C₁-C₄-alkyl)amino, a compound of formula (IIb)

in which X² represents hydrogen, cyano, nitro, C₁-C₄-alkyl,C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, or C₁-C₄-halogenoalkoxy; X³represents hydrogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl,C₁-C₄-alkoxy, or C₁-C₄-halogenoalkoxy; A² represents alkanediyl having 1or 2 carbon atoms that is optionally substituted by C₁-C₄-alkyl and/orC₁-C₄-alkoxy-carbonyl; and R¹⁵ represents hydroxyl, mercapto, amino,C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkylamino, ordi(C₁-C₄-alkyl)amino, a compound of formula (IIc)

in which R¹⁶ represents C₁-C₄-alkyl that is optionally substituted byfluorine, chlorine and/or bromine; R¹⁷ represents hydrogen, representsC₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,dioxolanyl-C₁-C₄-alkyl, furyl, furyl-C₁-C₄-alkyl, thienyl, thiazolyl, orpiperidinyl, each of which is optionally substituted by fluorine,chlorine, and/or bromine, or represents phenyl that is optionallysubstituted by fluorine, chlorine, and/or bromine or C₁-C₄-alkyl; andR¹⁸ represents hydrogen or represents C₁-C₆-alkyl, C₂-C₆-alkenyl orC₂-C₆-alkynyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, dioxolanyl-C₁-C₄-alkyl, furyl,furyl-C₁-C₄-alkyl, thienyl, thiazolyl, or piperidinyl, each of which isoptionally substituted by fluorine, chlorine, and/or bromine, orrepresents phenyl that is optionally substituted by fluorine, chlorine,and/or bromine or C₁-C₄-alkyl, or R¹⁸ together with R¹⁷ representsC₃-C₆-alkanediyl or C₂-C₅-oxaalkanediyl, each of which is optionallysubstituted by C₁-C₄-alkyl, phenyl, furyl, a fused benzene ring or bytwo substituents which, together with the C atom to which they arebonded, form a 5- or 6-membered carbocycle, a compound of formula (IId)

in which X⁴ represents nitro, cyano, carboxyl, carbamoyl, formyl,sulphamoyl, hydroxyl, amino, halogen, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl,C₁-C₄-alkoxy, or C₁-C₄-halogenoalkoxy; X⁵ represents nitro, cyano,carboxyl, carbamoyl, formyl, sulphamoyl, hydroxyl, amino, halogen,C₁-C₄-alkyl, C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, or C₁-C₄-halogenoalkoxy;n represents a number of between 0 and 5; R²² represents hydrogen orC₁-C₄-alkyl; R²³ represents hydrogen or C₁-C₄-alkyl; and R²⁴ representshydrogen, represents C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio,C₁-C₆-alkylamino, or di(C₁-C₄-alkyl)amino, each of which is optionallysubstituted by cyano, halogen, or C₁-C₄-alkoxy, or representsC₃-C₆-cycloalkyl, C₃-C₆-cycloalkyloxy, C₃-C₆-cycloalkylthio, orC₃-C₆-cycloalkylamino, each of which is optionally substituted by cyano,halogen, or C₁-C₄-alkyl, or a compound of formula (IIe)

in which X⁴ represents nitro, cyano, carboxyl, carbamoyl, formyl,sulphamoyl, hydroxyl, amino, halogen, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl,C₁-C₄-alkoxy, or C₁-C₄-halogenoalkoxy; X⁵ represents nitro, cyano,carboxyl, carbamoyl, formyl, sulphamoyl, hydroxyl, amino, halogen,C₁-C₄-alkyl, C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, or C₁-C₄-halogenoalkoxy;n represents a number of between 0 and 5; R²² represents hydrogen orC₁-C₄-alkyl; R²⁵ represents hydrogen, represents C₁-C₆-alkyl that isoptionally substituted by cyano, hydroxyl, halogen, or C₁-C₄-alkoxy,represents C₃-C₆-alkenyl or C₃-C₆-alkynyl, each of which is optionallysubstituted by cyano or halogen, or represents C₃-C₆-cycloalkyl that isoptionally substituted by cyano, halogen, or C₁-C₄-alkyl; R²⁶ representshydrogen, represents C₁-C₆-alkyl that is optionally substituted bycyano, hydroxyl, halogen, or C₁-C₄-alkoxy, represents C₃-C₆-alkenyl orC₃-C₆-alkynyl, each of which is optionally substituted by cyano orhalogen, represents C₃-C₆-cycloalkyl which is optionally substituted bycyano, halogen or C₁-C₄-alkyl, or represents phenyl that is optionallysubstituted by nitro, cyano, halogen, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl,C₁-C₄-alkoxy, or C₁-C₄-halogenoalkoxy, or R²⁶ together with R²⁵represents C₂-C₆-alkanediyl or C₂-C₅-oxaalkanediyl, each of which isoptionally substituted by C₁-C₄-alkyl.
 46. A composition according toclaim 45, in which the compound that improves crop plant tolerance isselected from the group consisting of the compounds cloquintocet-mexyl,fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyr-diethyl, furilazole,fenclorim, cumyluron, dymron, the compound

and the compound


47. A composition according to claim 45 in which the compound thatimproves crop plant tolerance is cloquintocet-mexyl or mefenpyr-diethyl.48. A pesticide and/or herbicide comprising one or more compounds offormula (I) according to claim
 36. 49. A method for controlling animalpests comprising allowing an effective amount of one or more compoundsof formula (I) according to claim 36 to act on pests and/or theirenvironment.
 50. A method for controlling undesired vegetationcomprising allowing an effective amount of one or more compounds offormula (I) according to claim 36 to act on plants and/or theirenvironment.
 51. A process for the preparation of a pesticide and/orherbicide comprising mixing one or more compounds of formula (I)according to claim 36 with one or more extenders and/or surface-activesubstances.
 52. A method for controlling undesired vegetation comprisingallowing an effective amount of a composition according to claim 45 toact on plants and/or their environment.
 53. A method for controllingundesired vegetation according to claim 51 in which the compound offormula (I) according to claim 36 and the compound that improves cropplant tolerance are allowed to act separately at short intervals onplants and/or their environment.